JP6149108B2 - Ceria-based composite polishing powder and method for producing the same - Google Patents
Ceria-based composite polishing powder and method for producing the same Download PDFInfo
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- JP6149108B2 JP6149108B2 JP2015518841A JP2015518841A JP6149108B2 JP 6149108 B2 JP6149108 B2 JP 6149108B2 JP 2015518841 A JP2015518841 A JP 2015518841A JP 2015518841 A JP2015518841 A JP 2015518841A JP 6149108 B2 JP6149108 B2 JP 6149108B2
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- 239000000843 powder Substances 0.000 title claims description 360
- 238000005498 polishing Methods 0.000 title claims description 203
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims description 156
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims description 156
- 239000002131 composite material Substances 0.000 title claims description 112
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000002002 slurry Substances 0.000 claims description 97
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 90
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 90
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 90
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 90
- 239000000395 magnesium oxide Substances 0.000 claims description 78
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 78
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 78
- 239000002243 precursor Substances 0.000 claims description 78
- 239000011259 mixed solution Substances 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 59
- 239000000047 product Substances 0.000 claims description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 239000006185 dispersion Substances 0.000 claims description 37
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000011737 fluorine Substances 0.000 claims description 34
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 31
- 239000011777 magnesium Substances 0.000 claims description 31
- 229910052749 magnesium Inorganic materials 0.000 claims description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- 229910052684 Cerium Inorganic materials 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- 239000011775 sodium fluoride Substances 0.000 claims description 18
- 235000013024 sodium fluoride Nutrition 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 63
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 30
- 150000002910 rare earth metals Chemical class 0.000 description 28
- 230000007797 corrosion Effects 0.000 description 27
- 238000005260 corrosion Methods 0.000 description 27
- 238000002474 experimental method Methods 0.000 description 23
- 239000005357 flat glass Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 16
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- -1 fluorine ions Chemical class 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- CNERRGRDMYRHEV-UHFFFAOYSA-H [Cl-].[La+3].[Ce+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[La+3].[Ce+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] CNERRGRDMYRHEV-UHFFFAOYSA-H 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 8
- 239000004254 Ammonium phosphate Substances 0.000 description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 6
- 235000019289 ammonium phosphates Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- 229910000397 disodium phosphate Inorganic materials 0.000 description 5
- 235000019800 disodium phosphate Nutrition 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000001488 sodium phosphate Substances 0.000 description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 description 5
- 235000011008 sodium phosphates Nutrition 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- YLENEZYZPLSAAV-UHFFFAOYSA-N cerium lanthanum neodymium praseodymium Chemical compound [La][Ce][Nd][Pr] YLENEZYZPLSAAV-UHFFFAOYSA-N 0.000 description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- SNRTYSDHDIYREL-UHFFFAOYSA-E [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[La+3].[Ce+3].[Pr+3] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[La+3].[Ce+3].[Pr+3] SNRTYSDHDIYREL-UHFFFAOYSA-E 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Description
本発明はセリア系複合研磨粉およびその製造方法に関し、希土類材料分野に属する。 The present invention relates to a ceria-based composite polishing powder and a method for producing the same, and belongs to the field of rare earth materials.
前世紀の40年代から、セリア含有量の高い希土類研磨粉は酸化鉄の代わりにガラス研磨(polishing)に用いられるようになり、ガラス研磨工程において重要な工程材料の一つとなっている。伝統的な研磨粉に比べて、希土類研磨粉は研磨速度が速く、表面仕上げ度(surface finish)が高く、寿命が長いという利点を有するとともに、研磨の品質と作業環境を改善することができる。希土類研磨粉はその独特の化学機械的機能原理による高い研磨効率をもって、ガラス研磨材料の最も好適な選択として、ミラー、光学素子(レンズ、プリズム)、カラーテレビのスクリーン、フラットパネルディスプレイ用電子ガラス、ウエハ、ディスクガラス基板などの製品の研磨加工に広く利用されている。 Since the 1940s of the last century, rare earth polishing powder with high ceria content has been used for glass polishing instead of iron oxide, and has become one of the important process materials in the glass polishing process. Compared with traditional polishing powders, rare earth polishing powders have the advantages of high polishing speed, high surface finish and long life, and can improve the quality and working environment of polishing. Rare earth polishing powder has high polishing efficiency due to its unique chemical mechanical function principle, and the most suitable selection of glass polishing material is mirror, optical element (lens, prism), color TV screen, electronic glass for flat panel display, It is widely used for polishing of products such as wafers and disk glass substrates.
セリア(CeO2)は研磨粒子としての性能は、その化学的構成、純粋度に関わるばかりでなく、CeO2の結晶形態や、粒度分布、粒子サイズなどの指標に関係があるので、CeO2の製造工程におけるコントロールに対してより厳しく求められている。したがって、形態の真円度が高く、粒度分布が均一で、研磨能力が強いCeO2研磨材の開発は特に重要なことになる。現在の、CeO2の製造技術について多く報道されているが、顆粒の塊が多く、粒度が均一ではなく、性能の安定性が悪いなどの問題が多く存在し、CeO2研磨材の性能に影響をもたらしている。 Ceria performance as (CeO 2) abrasive particles, the chemical structure, not only concerning the purity degree of the crystal form and CeO 2, particle size distribution, since there is a relationship indicators such as particle size, of CeO 2 There is a stricter demand for control in the manufacturing process. Therefore, it is particularly important to develop a CeO 2 abrasive that has a high roundness, a uniform particle size distribution, and a strong polishing ability. There are a lot of reports about CeO 2 production technology at present, but there are many problems such as a large amount of granules, non-uniform particle size, and poor performance stability, affecting the performance of CeO 2 abrasives. Has brought.
研磨工程において、最も有害なのは、あまり固い粒子により機械の損害になり、さらに研磨表面でかき傷ができ、被研磨物の表面の欠陥度や粗度が増加されることである。弱い凝集塊の粒子でも被研磨物の表面品質に影響を与えることがある。 In the polishing process, what is most harmful is that too hard particles cause mechanical damage, and scratches can be made on the polishing surface, increasing the degree of defects and roughness of the surface of the object to be polished. Even weakly agglomerated particles can affect the surface quality of the workpiece.
本発明は、研磨性能が優れ、研磨工程をするときに研磨液における顆粒の分布が均一で、凝集塊が生じないセリア系複合研磨粉を提供することを目的とする。 An object of the present invention is to provide a ceria-based composite polishing powder that is excellent in polishing performance, has a uniform distribution of granules in a polishing liquid during a polishing step, and does not generate agglomerates.
本発明のもう1つの目的は、前記セリア系複合研磨粉の製造方法を提供することである。 Another object of the present invention is to provide a method for producing the ceria based composite polishing powder.
本発明の一側面によると、マグネシウムを、酸化マグネシウムで計算して0.005wt%〜5wt%含有するセリア系複合研磨粉を提供する。 According to one aspect of the present invention, there is provided a ceria-based composite polishing powder containing 0.005 wt% to 5 wt% of magnesium calculated with magnesium oxide.
さらに、マグネシウムの含有量は、酸化マグネシウムで計算して0.01wt%〜2wt%である。 Furthermore, the magnesium content is 0.01 wt% to 2 wt% calculated with magnesium oxide.
さらに、セリウム以外の希土元素の少なくとも一種類を含有する。 Furthermore, it contains at least one kind of rare earth elements other than cerium.
さらに、フッ素を0.2wt%〜8wt%含有する。 Furthermore, 0.2 wt%-8 wt% of fluorine is contained.
さらに、リン元素を0.1wt%〜5wt%含有する。 Furthermore, 0.1 wt%-5 wt% of phosphorus elements are contained.
さらに、セリアの含有量は40wt%〜99.99wt%である。 Furthermore, the content of ceria is 40 wt% to 99.99 wt%.
さらに、セリア系複合研磨粉のメジアン粒径D50は0.02〜5μmで、好ましくは0.5〜3μmである。 Additionally, the median particle diameter D 50 of the ceria composite abrasive powder is 0.02 to 5, preferably from 0.5 to 3 [mu] m.
本発明のもう一つの側面によると、セリア、マグネシウム及びセリウム以外の希土元素の少なくとも一種類を含むセリア系複合研磨粉であって、セリアの含有量は40wt%〜99.99wt%で、マグネシウム元素の含有量は、酸化マグネシウムで計算して0.005wt%〜5wt%で、セリウム以外の希土元素の少なくとも一種類の含有量は0〜59.995wt%であるセリア系複合研磨粉を提供する。 According to another aspect of the present invention, it is a ceria-based composite polishing powder containing at least one kind of rare earth elements other than ceria, magnesium and cerium, and the ceria content is 40 wt% to 99.99 wt%. Provided is a ceria-based composite polishing powder in which the element content is 0.005 wt% to 5 wt% calculated with magnesium oxide, and the content of at least one rare earth element other than cerium is 0 to 59.995 wt% To do.
さらに、マグネシウムの含有量は、酸化マグネシウムで計算して0.01wt%〜2wt%である。 Furthermore, the magnesium content is 0.01 wt% to 2 wt% calculated with magnesium oxide.
さらに、フッ素を0.2wt%〜8wt%含有する。 Furthermore, 0.2 wt%-8 wt% of fluorine is contained.
さらに、リンを0.1wt%〜5wt%含有する。 Furthermore, 0.1 wt%-5 wt% of phosphorus is contained.
さらに、セリア系複合研磨粉のメジアン粒径D50は0.02〜5μmで、好ましくは0.5〜3μmである。 Additionally, the median particle diameter D 50 of the ceria composite abrasive powder is 0.02 to 5, preferably from 0.5 to 3 [mu] m.
本発明のもう一つの側面によると、上記セリア系複合研磨粉の製造方法を提供する。当該製造方法は、(1)研磨粉の主要成分であるセリウムを含有する塩溶液をむらなく混合するステップと、(2)炭酸水素マグネシウム溶液を沈殿剤として、ステップ(1)の混合溶液にむらなく混合させ、スラリーを得るステップと、(3)ステップ(2)のスラリーを30℃〜90℃で保温しながら0〜48hエイジングし、濾過して研磨粉の前駆体粉体を得るステップと、(4)前駆体粉体を600℃〜1000℃でバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品を得るステップとを含む。 According to another aspect of the present invention, there is provided a method for producing the above ceria based composite abrasive powder. The manufacturing method includes (1) a step of uniformly mixing a salt solution containing cerium, which is a main component of the abrasive powder, and (2) an uneven solution in the mixed solution of step (1) using a magnesium bicarbonate solution as a precipitant. A step of obtaining a slurry, and a step of (3) aging the slurry of step (2) at 30 ° C. to 90 ° C. for 0 to 48 h while filtering and filtering to obtain a precursor powder of an abrasive powder, (4) The precursor powder is burned at 600 ° C. to 1000 ° C., and after dispersion of the obtained powder and post-selection processing, a ceria composite abrasive powder product is obtained.
さらに、ステップ(1)における塩溶液は硝酸塩、硫酸塩又は塩化物溶液である。 Furthermore, the salt solution in step (1) is a nitrate, sulfate or chloride solution.
さらに、ステップ(2)における炭酸水素マグネシウムの水溶液の濃度は、酸化マグネシウムで計算して5〜25g/Lである。 Furthermore, the density | concentration of the aqueous solution of magnesium hydrogencarbonate in step (2) is 5-25 g / L calculated with magnesium oxide.
さらに、ステップ(2)における沈殿剤の使用量は、理論量の100〜130%であり、沈殿温度は15℃〜30℃で、撹拌時間は0.5〜5hである。 Further, the amount of the precipitating agent used in step (2) is 100 to 130% of the theoretical amount, the precipitation temperature is 15 ° C. to 30 ° C., and the stirring time is 0.5 to 5 h.
さらに、ステップ(2)の沈殿工程において、混合溶液へ界面活性剤であるポリエチレングリコールまたはエチレングリコールを添加し、むらなく混合させ、界面活性剤の添加量は、研磨粉の理論重量の0.1〜5.0wt%である。 Furthermore, in the precipitation step of step (2), polyethylene glycol or ethylene glycol, which is a surfactant, is added to the mixed solution and mixed uniformly. The amount of the surfactant added is 0.1% of the theoretical weight of the abrasive powder. -5.0 wt%.
さらに、ステップ(2)またはステップ(3)においてフッ素またはリンを含有する化合物を添加し、リンを含有する化合物はリン酸またはリン酸塩で、フッ素を含有する化合物はフッ化アンモニウム、フッ化水素酸、フッ化ケイ素酸ナトリウム及びフッ化ナトリウムの中の少なくとも一つである。 Further, in step (2) or step (3), a compound containing fluorine or phosphorus is added, the compound containing phosphorus is phosphoric acid or phosphate, and the compound containing fluorine is ammonium fluoride or hydrogen fluoride. At least one of acid, sodium fluorosiliconate and sodium fluoride.
さらに、沈殿及びロースト工程にて生成されたCO2が収集し回収され、炭酸水素マグネシウムの水溶液の製造に用いられる。 Furthermore, the CO 2 produced in the precipitation and roasting process is collected and recovered and used for the production of an aqueous solution of magnesium bicarbonate.
本発明のもう一つの側面によると、上記セリア系複合研磨粉の製造方法を提供する。当該製造方法は(1)研磨粉の主要成分であるセリウムを含有する塩溶液をむらなく混合し、混合溶液を得るステップと、(2)フッ素イオン及び/又はリン酸塩基を含有する水溶液を底層水として、まずフッ素または/およびリンと反応するのに必要とする理論量の50%〜100%の炭酸水素マグネシウムの水溶液を添加し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流で同時に加入し、混合し反応させてスラリーを得るステップと、(3)ステップ(2)のスラリーを30℃〜90℃で保温しながら0〜48hエイジングし、濾過、洗浄して研磨粉の前駆体粉体を得るステップと、(4)前駆体粉体を600℃〜1000℃でバーニングされて、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品を得るステップとを含む。 According to another aspect of the present invention, there is provided a method for producing the above ceria based composite abrasive powder. The manufacturing method includes (1) a step of uniformly mixing a salt solution containing cerium, which is a main component of the abrasive powder, to obtain a mixed solution, and (2) an aqueous solution containing fluorine ions and / or phosphate groups as a bottom layer. As water, first, an aqueous solution of magnesium hydrogen carbonate of 50% to 100% of the theoretical amount required to react with fluorine or / and phosphorus is added, and then the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are added. Are added at the same time in parallel flow, mixed and reacted to obtain a slurry, and (3) the slurry of step (2) is aged for 0 to 48 h while being kept at 30 ° C. to 90 ° C., filtered, washed and polished A step of obtaining a powder precursor powder, and (4) the precursor powder is burned at 600 ° C. to 1000 ° C., and is dispersed and selected for the obtained powder. Obtaining a combined abrasive powder product.
さらに、ステップ(1)における塩溶液は硝酸塩、硫酸塩または塩化物溶液で、塩溶液の稀土濃度はREOで計算して10〜300g/Lである。 Further, the salt solution in step (1) is a nitrate, sulfate or chloride solution, and the rare earth concentration of the salt solution is 10 to 300 g / L calculated by REO.
さらに、ステップ(2)における炭酸水素マグネシウムの水溶液の濃度は酸化マグネシウムで計算して5〜25g/Lである。 Furthermore, the density | concentration of the aqueous solution of magnesium hydrogencarbonate in step (2) is 5-25 g / L calculated with magnesium oxide.
さらに、ステップ(2)における炭酸水素マグネシウム溶液の合計使用量は理論量の100〜130%で、スラリーのpH値は5〜8であり、沈殿温度は15℃〜50℃で、撹拌時間は0.5〜5hである。 Further, the total amount of the magnesium hydrogen carbonate solution used in step (2) is 100 to 130% of the theoretical amount, the pH value of the slurry is 5 to 8, the precipitation temperature is 15 ° C. to 50 ° C., and the stirring time is 0. .5-5 h.
さらに、ステップ(2)の沈殿工程において、混合溶液へ界面活性剤であるポリエチレングリコールまたはエチレングリコールを添加し、むらなく混合させ、界面活性剤の添加量は、研磨粉の理論重量の0.1〜5.0wt%である。 Furthermore, in the precipitation step of step (2), polyethylene glycol or ethylene glycol, which is a surfactant, is added to the mixed solution and mixed uniformly. The amount of the surfactant added is 0.1% of the theoretical weight of the abrasive powder. -5.0 wt%.
さらに、ステップ(2)におけるリン酸塩基イオンを含有する水溶液はリン酸、リン酸ナトリウム、リン酸水素ナトリウム、リン酸アンモニウム、リン酸水素アンモニウム溶液の少なくとも一種類で、フッ素イオンを含有する溶液はフッ化アンモニウム、フッ化水素酸、フッ化ケイ素酸ナトリウム及びフッ化ナトリウムの水溶液の中の少なくとも一つである。 Furthermore, the aqueous solution containing phosphate basic ions in step (2) is at least one of phosphoric acid, sodium phosphate, sodium hydrogen phosphate, ammonium phosphate, and ammonium hydrogen phosphate solution, and the solution containing fluorine ions is At least one of an aqueous solution of ammonium fluoride, hydrofluoric acid, sodium fluorosilicate, and sodium fluoride.
さらに、ステップ(2)及びステップ(4)で生成したCO2は収集し、回収され、炭酸水素マグネシウムの水溶液の製造に用いる。 Further, the CO 2 produced in step (2) and step (4) is collected and recovered and used for the production of an aqueous solution of magnesium bicarbonate.
本発明の技術によると、セリア系複合研磨粉に微量のマグネシウムが導入され、研磨粉の研磨性能が大いに高められ、研磨粉のサスペンション性能が上昇し、研磨スラリーにおける顆粒の分布が均一ではなく凝集顆粒が生成されることが回避されている。 According to the technology of the present invention, a small amount of magnesium is introduced into the ceria-based composite polishing powder, the polishing performance of the polishing powder is greatly enhanced, the suspension performance of the polishing powder is increased, and the distribution of granules in the polishing slurry is not uniform but agglomerated Generation of granules is avoided.
本発明は炭酸水素マグネシウムを沈殿剤としてセリア系複合研磨粉の前駆体(炭酸セリウムなど)を製造し、沈殿工程において先に形成された少量なフッ化マグネシウムまたは/及びマグネシウムのリン酸塩は、研磨粉の結晶度を高め、球状化を促進し、粒度の分布が狭く、研磨粉スラリーの分散性とサスペンション性能を向上でき、研磨粉の研磨腐食能力を強化させ、研磨の引っ掻き傷率を低下させることができる。 The present invention produces a ceria-based composite polishing powder precursor (cerium carbonate or the like) using magnesium bicarbonate as a precipitating agent, and a small amount of magnesium fluoride and / or magnesium phosphate previously formed in the precipitation step is: Increases the crystallinity of the abrasive powder, promotes spheroidization, narrows the particle size distribution, improves the dispersibility and suspension performance of the abrasive slurry, enhances the abrasive corrosion ability of the abrasive powder, and reduces the scratch rate of polishing Can be made.
上記製造工程によると、最終的には、従来の製品とは異なる新しい研磨粉材料が得られ、当該セリア系稀土研磨粉には、マグネシウムを含むとともに、フッ素や、リンの少なくとも一種類を含む。当該セリウム系研磨粉に含まれるフッ素または/及びリンはマグネシウムと結合して、優れた相乗効果を有し、研磨粉の研磨腐食能力をさらに強化させ、球状化や分散性を促進し、粒度を減少することができ、研磨粉のスラリー製造のサスペンション性と均一性を向上させ、研磨の引っ掻き傷率を減少し、研磨粉の総合的な利用性能を高めることができる。 According to the above manufacturing process, finally, a new abrasive powder material different from the conventional product is obtained, and the ceria-based rare earth abrasive powder contains magnesium and at least one of fluorine and phosphorus. Fluorine and / or phosphorus contained in the cerium-based polishing powder combines with magnesium, has an excellent synergistic effect, further enhances the polishing corrosion ability of the polishing powder, promotes spheroidization and dispersibility, and increases the particle size. This can reduce the suspension and uniformity of the slurry production of the abrasive powder, reduce the scratch rate of polishing, and improve the overall utilization performance of the abrasive powder.
本発明は、炭酸水素マグネシウムの水溶液を沈殿剤としてセリア系研磨粉を製造し、環境に優しく、アンモニア態窒素の排出がないとともに、沈殿やロースト工程で生成したCO2が回収し利用され、低炭素排出を実現することができる。 The present invention produces a ceria-based abrasive powder using an aqueous solution of magnesium hydrogen carbonate as a precipitating agent, is environmentally friendly, does not discharge ammonia nitrogen, and collects and uses CO2 produced in precipitation and roasting processes, and is low in carbon. Emission can be realized.
なお、互いに衝突がない場合、本出願における実施例および実施例における特徴は互いに組み合わせることができる。以下、実施例を結合して本発明を詳しく説明する。 In addition, when there is no collision with each other, the embodiments in the present application and the features in the embodiments can be combined with each other. Hereinafter, the present invention will be described in detail with reference to examples.
本発明の代表的な実施形態によると、マグネシウムを、酸化マグネシウムで計算して0.005wt%〜5wt%含有するセリア系複合研磨粉を提供する。該セリア系複合研磨粉の製造方法は、(1)研磨粉の主要成分であるセリウムを含有する塩溶液をむらなく混合するステップと、(2)炭酸水素マグネシウムの水溶液を沈殿剤として、ステップ(1)の混合溶液にむらなく混合させ、スラリーを得るステップと、(3)ステップ(2)のスラリーを30℃〜90℃で保温しながら0〜48hエイジングし、濾過し洗浄して研磨粉の前駆体粉体を得るステップと、(4)前駆体粉体を600℃〜1000℃でバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品を得るステップとを含む。 According to an exemplary embodiment of the present invention, there is provided a ceria-based composite polishing powder containing 0.005 wt% to 5 wt% of magnesium calculated with magnesium oxide. The method for producing the ceria-based composite polishing powder includes (1) a step of uniformly mixing a salt solution containing cerium, which is a main component of the polishing powder, and (2) a step ( 1) Mixing the mixed solution evenly to obtain a slurry; (3) Aging the slurry of step (2) at 30 ° C. to 90 ° C. for 0 to 48 hours, filtering and washing, A step of obtaining a precursor powder, and (4) a step of obtaining a ceria-based composite abrasive powder product by subjecting the precursor powder to burning at 600 ° C. to 1000 ° C., followed by dispersion and sorting after the resulting powder. Including.
前記セリア系複合研磨粉に微量のマグネシウム元素が導入され、マグネシウムにより研磨粉スラリーにおけるZata電位をよりマイナスになり、研磨粉スラリーの凝集性を低減させ、マグネシウム元素を添加することで、硬い粒子を消去できる。かつ2価マグネシウムにより4価セリウムの研磨粉が被加工材とより吸着しやすくなり、研磨粉の性能は研磨粉と被加工材との吸着に強く依存するため、両者の緊密な吸着は、研磨効果を効果的に改善することができる。また、一部のセリウムイオンがマグネシウムイオンに置換され、そのラティスが一部歪みを発生し、その化学的活性が増加することになる。マグネシウムのドーピングで、研磨粉の表面の球状化を高め、研磨粉の研磨性能を向上させることができ、また、マグネシウム元素の添加により、研磨粉のサスペンション性能を改善でき、研磨スラリーにおける顆粒の分布が均一でなく凝集顆粒を生じることを避けることができる。 A small amount of magnesium element is introduced into the ceria-based composite polishing powder, and the Zata potential in the polishing powder slurry is made more negative by magnesium, reducing the cohesiveness of the polishing slurry, and adding magnesium element to hard particles. Can be erased. In addition, divalent magnesium makes it easier for the tetravalent cerium abrasive powder to adsorb to the workpiece, and the performance of the abrasive powder strongly depends on the adsorption of the abrasive powder to the workpiece. The effect can be improved effectively. In addition, some cerium ions are replaced with magnesium ions, the lattice is partially distorted, and the chemical activity is increased. Magnesium doping can increase the spheroidization of the surface of the polishing powder and improve the polishing performance of the polishing powder. Addition of magnesium element can improve the suspension performance of the polishing powder, and the distribution of granules in the polishing slurry. Is not uniform and agglomerated granules can be avoided.
反応において、過量な炭酸水素マグネシウムを添加し、加熱することで、過量な炭酸水素マグネシウムを、炭酸マグネシウム沈殿として分解させ、炭酸マグネシウムを炭酸セリウム沈殿に均一に分布させ、ローストして所定量の酸化マグネシウムを含有するセリア系複合研磨粉が得られる。 In the reaction, an excessive amount of magnesium hydrogen carbonate is added and heated to decompose the excessive amount of magnesium hydrogen carbonate as a magnesium carbonate precipitate, and the magnesium carbonate is uniformly distributed in the cerium carbonate precipitate and roasted to a predetermined amount of oxidation. A ceria-based composite polishing powder containing magnesium is obtained.
様々な被研磨物に対して、セリアの含有量が異なる複合研磨粉を採用することができる。そのセリアの含有量は、40wt%〜99.99wt%である。
前記セリア系複合研磨粉のメジアン粒径D50は0.02〜5μmで、好ましくは0.5〜3μmである。
Composite polishing powders having different ceria contents can be used for various objects to be polished. The ceria content is 40 wt% to 99.99 wt%.
The median particle size D 50 of the ceria based composite polishing powder is 0.02 to 5 μm, preferably 0.5 to 3 μm.
前記ステップ(1)における塩溶液は硝酸塩、塩酸塩、または硫酸塩溶液である。 The salt solution in the step (1) is a nitrate, hydrochloride, or sulfate solution.
前記ステップ(2)における炭酸水素マグネシウム溶液の濃度は、酸化マグネシウムで計算して5〜25g/Lである。 The concentration of the magnesium hydrogen carbonate solution in step (2) is 5 to 25 g / L calculated with magnesium oxide.
前記ステップ(2)における沈殿剤の使用量は、理論量の100〜130%であり、沈殿温度は15℃〜30℃で、撹拌時間は0.5〜5hである。 The amount of the precipitant used in step (2) is 100 to 130% of the theoretical amount, the precipitation temperature is 15 ° C. to 30 ° C., and the stirring time is 0.5 to 5 h.
前記ステップ(2)の沈殿工程において、混合溶液へポリエチレングリコールまたはエチレングリコールなどの界面活性剤を添加剤として添加し、むらなく混合させ、界面活性剤の添加量は、研磨粉の理論重量の0.1〜5.0wt%である。 In the precipitation step of step (2), a surfactant such as polyethylene glycol or ethylene glycol is added to the mixed solution as an additive and mixed uniformly. The amount of the surfactant added is 0 of the theoretical weight of the polishing powder. .1 to 5.0 wt%.
前記ステップ(2)において、リン酸塩基イオンを含有する水溶液はリン酸またはリン酸塩で、前記フッ素イオンを含有する水溶液はフッ化アンモニウム、フッ化水素酸、フッ化ケイ素酸ナトリウム及びフッ化ナトリウム溶液の中の少なくとも一つである。 In the step (2), the aqueous solution containing phosphate basic ions is phosphoric acid or phosphate, and the aqueous solution containing fluorine ions is ammonium fluoride, hydrofluoric acid, sodium fluoride siliconate and sodium fluoride. At least one of the solutions.
本発明のある代表的な実施形態によると、セリア、マグネシウム元素及びセリウム以外の希土元素の少なくとも一種類を含むセリア系複合研磨粉であって、セリアの含有量は40wt%〜99.99wt%で、マグネシウム元素の含有量は、酸化マグネシウムで計算して0.005wt%〜5wt%で、セリウム以外の希土元素の少なくとも一種類の含有量は0〜59.995wt%であるセリア系複合研磨粉を提供する。該セリア系複合研磨粉の製造方法は、(1)研磨粉の主要成分であるセリウムを含有する塩溶液をむらなく混合し、混合溶液を得るステップと、(2)フッ素イオン及び/又はリン酸塩基イオンを含有する水溶液を底層水として、まずフッ素または/およびリンと反応するのに必要とする理論量の50%〜100%の炭酸水素マグネシウム溶液を添加し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流で同時に加入し、混合し反応させてスラリーを得るステップと、(3)ステップ(2)のスラリーを30℃〜90℃で保温しながら0〜48hエイジングし、濾過し洗浄して研磨粉の前駆体粉体を得るステップと、(4)前駆体粉体を600℃〜1000℃でバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品を得るステップとを含む。 According to an exemplary embodiment of the present invention, a ceria-based composite polishing powder containing at least one kind of ceria, a magnesium element, and a rare earth element other than cerium, wherein the ceria content is 40 wt% to 99.99 wt%. The content of magnesium element is 0.005 wt% to 5 wt% calculated with magnesium oxide, and the content of at least one kind of rare earth elements other than cerium is 0 to 59.995 wt%. Provide powder. The method for producing the ceria-based composite polishing powder includes (1) a step of uniformly mixing a salt solution containing cerium, which is a main component of the polishing powder, to obtain a mixed solution, and (2) fluorine ions and / or phosphoric acid. First, a 50% to 100% magnesium hydrogen carbonate solution of a theoretical amount necessary for reacting with fluorine or / and phosphorus is added using an aqueous solution containing base ions as the bottom layer water, and then the mixed solution of step (1) And the aqueous solution of magnesium hydrogen carbonate are added simultaneously in the same flow, mixed and reacted to obtain a slurry, and (3) the slurry of step (2) is aged for 0 to 48 h while being kept at 30 to 90 ° C. Filtering and washing to obtain a polishing powder precursor powder, and (4) dispersing and sorting the precursor powder by burning at 600 ° C. to 1000 ° C. And a post-treatment to obtain a ceria-based composite abrasive powder product.
前記セリア系複合研磨粉に微量のマグネシウム元素が導入され、マグネシウムにより研磨粉スラリーにおけるZata電位をよりマイナスになり、研磨粉スラリーの凝集性を低減させ、マグネシウム元素を添加することで、硬い粒子を消去できる。かつ2価マグネシウムにより4価セリウムの研磨粉が被加工材とより吸着しやすくなり、研磨粉の性能は研磨粉と被加工材との吸着に強く依存するため、両者の緊密な吸着は、研磨効果を効果的に改善することができる。また、一部のセリウムイオンがマグネシウムイオンに置換され、そのラティスが一部歪みを発生し、その化学的活性が増加することになる。マグネシウムのドーピングで、研磨粉の表面の球状化を高め、研磨粉の研磨性能を向上させることができ、また、マグネシウム元素の添加により、研磨粉のサスペンション性能を改善でき、研磨スラリーにおける顆粒の分布が均一でなく凝集顆粒を生じることを避けることができる。前記セリア系複合研磨粉のメジアン粒径D50は0.02〜5μmで、好ましくは0.5〜3μmであり、粒度分布(D90−D10)/2D50≦1で、研磨粉の粒度分布が狭く、研磨の引っ掻き傷率の低減に有利である。 A small amount of magnesium element is introduced into the ceria-based composite polishing powder, and the Zata potential in the polishing powder slurry is made more negative by magnesium, reducing the cohesiveness of the polishing slurry, and adding magnesium element to hard particles. Can be erased. In addition, divalent magnesium makes it easier for the tetravalent cerium abrasive powder to adsorb to the workpiece, and the performance of the abrasive powder strongly depends on the adsorption of the abrasive powder to the workpiece. The effect can be improved effectively. In addition, some cerium ions are replaced with magnesium ions, the lattice is partially distorted, and the chemical activity is increased. Magnesium doping can increase the spheroidization of the surface of the polishing powder and improve the polishing performance of the polishing powder. Addition of magnesium element can improve the suspension performance of the polishing powder, and the distribution of granules in the polishing slurry. Is not uniform and agglomerated granules can be avoided. The median particle size D 50 of the ceria-based composite polishing powder is 0.02 to 5 μm, preferably 0.5 to 3 μm, and the particle size distribution (D90-D 10 ) / 2D 50 ≦ 1, and the particle size distribution of the polishing powder. Is narrow, which is advantageous for reducing the scratch rate of polishing.
また、上記方法によると、炭酸水素マグネシウムを沈殿剤としてセリア系複合研磨粉の前駆体(炭酸セリウムなど)を製造し、沈殿工程において先に形成された少量なフッ化マグネシウムまたは/及びマグネシウムのリン酸塩は、研磨粉の結晶度を高め、球状化を促進し、粒度の分布が狭く、研磨粉スラリーの分散性とサスペンション性能を向上でき、研磨粉の研磨腐食能力を強化させ、研磨の引っ掻き傷率を低下させることができる。 In addition, according to the above method, a precursor (such as cerium carbonate) of a ceria-based composite polishing powder is produced using magnesium hydrogen carbonate as a precipitant, and a small amount of magnesium fluoride and / or magnesium phosphorus previously formed in the precipitation step. Acid salt increases the crystallinity of the abrasive powder, promotes spheroidization, narrows the particle size distribution, improves the dispersibility and suspension performance of the abrasive slurry, enhances the abrasive corrosion ability of the abrasive powder, and scratches the abrasive The scratch rate can be reduced.
反応において、過量な炭酸水素マグネシウムを添加し、加熱することで、過量な炭酸水素マグネシウムを、炭酸マグネシウム沈殿として分解させ、炭酸マグネシウムを炭酸セリウム沈殿に均一に分布させ、ローストをして所定量の酸化マグネシウムを含有するセリア系複合研磨粉が得られる。 In the reaction, an excessive amount of magnesium hydrogen carbonate is added and heated to decompose the excessive amount of magnesium hydrogen carbonate as a magnesium carbonate precipitate, and the magnesium carbonate is uniformly distributed in the cerium carbonate precipitate and roasted to obtain a predetermined amount. A ceria-based composite polishing powder containing magnesium oxide is obtained.
ステップ(1)における塩溶液は硝酸塩、硫酸塩または塩化物溶液で、塩溶液の稀土濃度はREOで計算して10〜300g/Lであることが好ましい。 The salt solution in step (1) is a nitrate, sulfate or chloride solution, and the rare earth concentration of the salt solution is preferably 10 to 300 g / L calculated by REO.
ステップ(2)における炭酸水素マグネシウム溶液の濃度は酸化マグネシウムで計算して5〜25g/Lであることが好ましい。 The concentration of the magnesium hydrogen carbonate solution in step (2) is preferably 5 to 25 g / L calculated with magnesium oxide.
ステップ(2)における沈殿剤の使用量は理論量の100〜130%で、スラリーのpH値は5〜8であり、沈殿温度は15℃〜50℃で、撹拌時間は0.5〜5hであることが好ましい。炭酸水素マグネシウムでセリア−ジルコニアを沈殿する場合、pH値は5〜8にすることができる。 The amount of the precipitating agent used in step (2) is 100 to 130% of the theoretical amount, the pH value of the slurry is 5 to 8, the precipitation temperature is 15 ° C. to 50 ° C., and the stirring time is 0.5 to 5 h. Preferably there is. When ceria-zirconia is precipitated with magnesium bicarbonate, the pH value can be 5-8.
ステップ(2)の沈殿工程において、混合溶液へ界面活性剤であるポリエチレングリコールまたはエチレングリコールを添加し、むらなく混合させ、界面活性剤の添加量は、研磨粉の理論重量の0.1〜5.0wt%であることが好ましい。 In the precipitation step of step (2), polyethylene glycol or ethylene glycol, which is a surfactant, is added to the mixed solution and mixed uniformly. The amount of the surfactant added is 0.1 to 5 of the theoretical weight of the abrasive powder. 0.0 wt% is preferable.
ステップ(2)におけるリン酸塩基イオンを含有する水溶液はリン酸、リン酸ナトリウム、リン酸水素ナトリウム、リン酸アンモニウム、リン酸水素アンモニウム溶液の少なくとも一種類で、その中に、特にリン酸アンモニウム、リン酸水素アンモニウムはマグネシウムイオンと反応して安定したリン酸マグネシウムアンモニウム沈殿を生成でき、フッ素イオンを含有する溶液はフッ化アンモニウム、フッ化水素酸、フッ化ケイ素酸ナトリウム及びフッ化ナトリウムの水溶液の中の少なくとも一つである。 The aqueous solution containing phosphate basic ions in step (2) is at least one of phosphoric acid, sodium phosphate, sodium hydrogen phosphate, ammonium phosphate, and ammonium hydrogen phosphate solution, among which ammonium phosphate, Ammonium hydrogen phosphate can react with magnesium ions to form a stable magnesium ammonium phosphate precipitate, and the solution containing fluoride ions can be an aqueous solution of ammonium fluoride, hydrofluoric acid, sodium fluoride siliconate and sodium fluoride. At least one of them.
ステップ(2)及びステップ(4)で生成したCO2は収集し回収され、炭酸水素マグネシウム溶液の製造に用いる。 The CO 2 produced in step (2) and step (4) is collected and recovered and used for the production of magnesium bicarbonate solution.
以下、実施例を参照して、本発明をさらに説明する。 Hereinafter, the present invention will be further described with reference to examples.
実施例1
(1)塩化ランタンセリウム混合溶液と炭酸水素マグネシウム溶液とを均一な速度で同時に反応装置に加入し、少量なフッ化アンモニウムを添加する。炭酸水素マグネシウムの加入量は、理論量の110%で、反応温度は25℃で、3h撹拌して、むらなく混合させて、スラリーが得られる。
Example 1
(1) A lanthanum cerium chloride mixed solution and a magnesium hydrogen carbonate solution are simultaneously added to the reactor at a uniform rate, and a small amount of ammonium fluoride is added. The amount of magnesium hydrogen carbonate added is 110% of the theoretical amount, the reaction temperature is 25 ° C., and the mixture is stirred for 3 hours and mixed uniformly to obtain a slurry.
(2)ステップ(1)のスラリーを60℃で保温しながら12hエージングして、濾過や、洗浄、乾燥を経て、研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 12 hours while keeping the temperature at 60 ° C., and after filtration, washing and drying, a precursor powder of an abrasive powder is obtained.
(3)上記前駆体粉体を900℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は63.3wt%で、酸化マグネシウムの含有量は0.01wt%、フッ素の含有量は2.2wt%で、当該研磨粉のD50は2.6μmである。 (3) The precursor powder is burned at 900 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 63.3 wt%, the content of magnesium oxide is 0.01 wt%, the content of fluorine is 2.2 wt%, and the D 50 of the polishing powder is 2.6 μm.
得られるセリア系複合研磨粉をスラリーに調製して(pulp conditioning)、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.48mg/minに達し、同種類製品に比べて優れた表面仕上げ度が示されている。 The resulting ceria-based composite polishing powder was prepared into a slurry (pulp conditioning), and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.48 mg / min, which was higher than that of the same type product. Excellent surface finish.
比較実施例1(従来の工程による製造)
(1)塩化ランタンセリウム混合溶液と炭酸水素アンモニウムの水溶液とを均一な速度で同時に反応装置に加入し、少量なフッ化アンモニウムを添加する。炭酸水素アンモニウムの加入量は、理論量の110%で、反応温度は25℃で、3h撹拌して、むらなく混合させて、スラリーが得られる。
Comparative Example 1 (Manufacturing by conventional process)
(1) A lanthanum cerium chloride mixed solution and an aqueous solution of ammonium hydrogen carbonate are simultaneously added to the reactor at a uniform rate, and a small amount of ammonium fluoride is added. The amount of ammonium hydrogen carbonate added is 110% of the theoretical amount, the reaction temperature is 25 ° C., and the mixture is stirred for 3 hours and mixed uniformly to obtain a slurry.
(2)ステップ(1)のスラリーを60℃で保温しながら12hエージングして、濾過や、洗浄、乾燥を経て、研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 12 hours while keeping the temperature at 60 ° C., and after filtration, washing and drying, a precursor powder of an abrasive powder is obtained.
(3)上記前駆体粉体を900℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は63.3wt%で、酸化マグネシウムの含有量は0wt%、フッ素の含有量は2.2wt%で、当該研磨粉のD50は3.5μmである。 (3) The precursor powder is burned at 900 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 63.3 wt%, the content of magnesium oxide is 0 wt%, the content of fluorine is 2.2 wt%, and D 50 of the polishing powder is 3.5 μm.
得られるセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.43mg/minに達し、その表面仕上げ度が同種類製品に近いことが示されている。 The resulting ceria-based composite polishing powder was prepared into a slurry, and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.43 mg / min, and the surface finish was the same kind of product. It is shown to be close.
実施例2
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製し、稀土含有量はREO(稀土酸化物)で計算して120g/Lである。
Example 2
(1) A mixed solution of cerium chloride and lanthanum chloride is prepared in a predetermined ratio, and the rare earth content is 120 g / L calculated by REO (rare earth oxide).
(2)炭酸水素マグネシウムの水溶液を沈殿剤として、濃度(酸化マグネシウムで計算)15g/Lの沈殿剤を均一な速度でステップ(1)の混合溶液に加入し、沈殿させる。炭酸水素マグネシウムの加入量は理論量の105%で、反応温度は20℃、0.5h撹拌して、スラリーが得られる。スラリーに研磨粉の理論重量の2%のポリエチレングリコールを添加してむらなく混合させる。 (2) Using an aqueous solution of magnesium hydrogen carbonate as a precipitating agent, a precipitating agent having a concentration (calculated with magnesium oxide) of 15 g / L is added to the mixed solution in step (1) at a uniform rate to cause precipitation. The amount of magnesium hydrogen carbonate added is 105% of the theoretical amount, the reaction temperature is 20 ° C., and the mixture is stirred for 0.5 h to obtain a slurry. Polyethylene glycol of 2% of the theoretical weight of the abrasive powder is added to the slurry and mixed uniformly.
(3)ステップ(2)の混合スラリーを50℃で保温しながら24hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (3) The mixed slurry of step (2) is aged for 24 hours while being kept at 50 ° C., and a precursor powder of an abrasive powder is obtained through filtration, washing and drying.
(4)上記前駆体粉体を1000℃で3hバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は62wt%で、酸化マグネシウムの含有量は0.005wt%、当該研磨粉のD50は4.8μmである。 (4) The precursor powder is burned at 1000 ° C. for 3 hours, and after the dispersion and selection of the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 62 wt%, the content of magnesium oxide is 0.005 wt%, and the D 50 of the polishing powder is 4.8 μm.
実施例3
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製し、稀土含有量はREOで計算して150g/Lである。
Example 3
(1) A mixed solution of cerium chloride and lanthanum chloride is prepared at a predetermined ratio, and the rare earth content is 150 g / L calculated by REO.
(2)炭酸水素マグネシウム溶液を沈殿剤として、濃度(酸化マグネシウムで計算)5g/Lの沈殿剤を均一な速度でステップ(1)の混合溶液に加入し、沈殿させる。炭酸水素マグネシウムの加入量は理論量の105%で、反応温度は20℃、3h撹拌して、スラリーが得られる。スラリーに研磨粉の理論重量の5%のポリエチレングリコールを添加してむらなく混合させ、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) Using a magnesium hydrogen carbonate solution as a precipitant, a precipitant having a concentration (calculated with magnesium oxide) of 5 g / L is added to the mixed solution in step (1) at a uniform rate to cause precipitation. The amount of magnesium hydrogen carbonate added is 105% of the theoretical amount, the reaction temperature is 20 ° C., and the mixture is stirred for 3 hours to obtain a slurry. Polyethylene glycol of 5% of the theoretical weight of the abrasive powder is added to the slurry and mixed uniformly, and a precursor powder of the abrasive powder is obtained through filtration, washing and drying.
(3)上記前駆体粉体を950℃で4hバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は62wt%で、酸化マグネシウムの含有量は0.05wt%、当該研磨粉のD50は2.5μmである。 (3) The precursor powder is burned at 950 ° C. for 4 hours, and after the dispersion and selection of the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 62 wt%, the content of magnesium oxide is 0.05 wt%, and the D 50 of the polishing powder is 2.5 μm.
実施例4
(1)炭酸水素マグネシウム溶液(酸化マグネシウムで計算して20g/Lである)と塩化セリウムランタン混合溶液(REOで計算して100g/L)とを所定の速度で連続して反応釜に加入し、炭酸水素マグネシウムの加入量は理論量の115%で、反応温度は25℃で、材料が反応釜に10min留まってから、熟成タンクに入り、70℃で2hエージングしてから、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。
Example 4
(1) Magnesium bicarbonate solution (calculated with magnesium oxide is 20 g / L) and cerium lanthanum chloride mixed solution (100 g / L calculated with REO) are continuously added to the reaction kettle at a predetermined rate. The amount of magnesium bicarbonate added is 115% of the theoretical amount, the reaction temperature is 25 ° C., the material stays in the reaction kettle for 10 min, enters the aging tank and is aged at 70 ° C. for 2 hours, and then filtered and washed. The precursor powder of the abrasive powder is obtained through drying.
(2)上記前駆体粉体を700℃で8hバーニングされて、得られる粉体に対する分散、選別を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は60wt%で、酸化マグネシウムの含有量は0.5wt%、当該研磨粉のD50は1.2μmである。 (2) The precursor powder is burned at 700 ° C. for 8 hours, and after dispersion and selection with respect to the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 60 wt%, the content of magnesium oxide is 0.5 wt%, and the D 50 of the polishing powder is 1.2 μm.
実施例5
(1)炭酸水素マグネシウム溶液(酸化マグネシウムで計算して15g/Lである)と塩化セリウム混合溶液(REOで計算して100g/L)とを所定の速度で連続して反応釜に加入し、炭酸水素マグネシウムの加入量は理論量の102%で、反応温度は35℃で、材料が反応釜に10min留まってから、熟成タンクに入り、60℃で5hエージングしてから、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。
Example 5
(1) A magnesium hydrogen carbonate solution (calculated with magnesium oxide is 15 g / L) and a cerium chloride mixed solution (100 g / L calculated with REO) are continuously added to the reaction kettle at a predetermined rate, The amount of magnesium hydrogen carbonate added is 102% of the theoretical amount, the reaction temperature is 35 ° C., the material stays in the reaction kettle for 10 min, enters the aging tank, aged at 60 ° C. for 5 h, filtered, washed, A precursor powder of an abrasive powder is obtained through drying.
(2)上記前駆体粉体を850℃で6hバーニングされて、得られる粉体に対する分散、選別を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は99.99wt%で、酸化マグネシウムの含有量は0.005wt%、当該研磨粉のD50は2.3μmである。 (2) The precursor powder is burned at 850 ° C. for 6 hours, and after dispersion and selection with respect to the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 99.99 wt%, the content of magnesium oxide is 0.005 wt%, and the D 50 of the polishing powder is 2.3 μm.
実施例6
(1)塩化ランタンセリウムプラセオジムネオジム混合溶液と炭酸水素マグネシウム溶液とを所定の速度で同時に反応装置に加入するとともに、少量なフッ化水素を加入し、炭酸水素マグネシウムの加入量は理論量の130%で、反応温度は15℃、2h撹拌してスリラーが得られる。
Example 6
(1) A lanthanum cerium praseodymium neodymium mixed solution and a magnesium hydrogen carbonate solution are simultaneously added to the reactor at a predetermined rate, and a small amount of hydrogen fluoride is added. The amount of magnesium hydrogen carbonate added is 130% of the theoretical amount. Then, the reaction temperature is 15 ° C. and the mixture is stirred for 2 hours to obtain a thriller.
(2)ステップ(1)のスラリーを30℃で保温しながら48hエイジングし、濾過や、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 48 hours while being kept at 30 ° C., and a precursor powder of polishing powder is obtained through filtration and drying.
(3)上記前駆体粉体を950℃で6hバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は40.5wt%で、酸化マグネシウムの含有量は4.8wt%、フッ素の含有量は0.2wt%で、当該研磨粉のD50は3.8μmである。 (3) The precursor powder is burned at 950 ° C. for 6 hours, and after the dispersion and selection of the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 40.5 wt%, the content of magnesium oxide is 4.8 wt%, the content of fluorine is 0.2 wt%, and the D 50 of the polishing powder is 3.8 μm.
実施例7
(1)塩化セリウム溶液と炭酸水素マグネシウムの水溶液とを均一な速度で同時に反応装置に加入し、反応温度は55℃で、2h撹拌してから、フッ化ナトリウムを加入し、混合させてスリラーが得られる。
Example 7
(1) A cerium chloride solution and an aqueous solution of magnesium hydrogen carbonate are simultaneously added to the reactor at a uniform speed, the reaction temperature is 55 ° C., and the mixture is stirred for 2 hours. can get.
(2)スラリーを60℃で保温しながら5hエイジングし、濾過や、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) The slurry is aged at 60 ° C. for 5 hours, and a precursor powder of an abrasive powder is obtained through filtration and drying.
(3)上記前駆体粉体を800℃で4hバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は96.7wt%で、プラセオジミアの含有量は1wt%で、酸化マグネシウムの含有量は1wt%、フッ素の含有量は1.2wt%で、当該研磨粉のD50は3.3μmである。 (3) The precursor powder is burned at 800 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. The content of ceria therein is 96.7wt%, the content of praseodymia is 1 wt%, the content of magnesium oxide is 1 wt%, the content of fluorine at 1.2 wt%, D 50 of the polishing powder 3.3 μm.
実施例8
(1)炭酸水素マグネシウムを沈殿剤として、その使用量は理論量の110%で、硫酸セリウム溶液を沈殿剤に加入して反応させてスリラーが形成される。
Example 8
(1) Using magnesium hydrogen carbonate as a precipitating agent, the amount used is 110% of the theoretical amount, and a cerium sulfate solution is added to the precipitating agent and reacted to form a thriller.
(2)ステップ(1)のスラリーを90℃で保温しながら2hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。
(3)上記前駆体粉体を600℃で10hバーニングされて、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は99.9wt%で、酸化マグネシウムの含有量は1.15wt%で、当該研磨粉のD50は1.2μmである。
(2) The slurry in step (1) is aged for 2 h while being kept at 90 ° C., and a precursor powder of an abrasive powder is obtained through filtration, washing and drying.
(3) The precursor powder is burned at 600 ° C. for 10 hours, and after the dispersion and selection of the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 99.9 wt%, the content of magnesium oxide is 1.15 wt%, and the D 50 of the polishing powder is 1.2 μm.
実施例9
(1)硝酸セリウム、硝酸ランタンを所定の比率で混合溶液に調製する(REOで計算して200g/L)。
Example 9
(1) Prepare a mixed solution of cerium nitrate and lanthanum nitrate at a predetermined ratio (200 g / L calculated by REO).
(2)炭酸水素マグネシウム溶液(酸化マグネシウムで計算して12g/L)を沈殿剤として、その使用量は理論量の115%であり、それをステップ(1)の混合溶液と共沈法で反応させてスラリーが得られ、当該スラリーに研磨粉理論重量の3.1%の界面活性剤であるエチレングリコールを添加して、むらなく混合させる。 (2) Magnesium hydrogen carbonate solution (12 g / L calculated with magnesium oxide) is used as a precipitating agent, and the amount used is 115% of the theoretical amount, and this is reacted with the mixed solution in step (1) by the coprecipitation method. Thus, a slurry is obtained, and ethylene glycol, which is a surfactant of 3.1% of the theoretical weight of the polishing powder, is added to the slurry and mixed uniformly.
(3)ステップ(2)の混合スリラーを80℃で保温しながら5hエージングして、その中にフッ化アンモニウムを添加し、むらなく混合させ、濾過や乾燥してから、研磨粉の前駆体粉体が得られる。 (3) The mixed chiller of step (2) is aged for 5 hours while keeping at 80 ° C., and ammonium fluoride is added therein, mixed uniformly, filtered and dried, and then the precursor powder of the abrasive powder The body is obtained.
(4)前記前駆体粉体を750℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は70wt%で、酸化マグネシウムの含有量は1.5wt%で、フッ素の含有量は6.8wt%で、当該研磨粉のD50は0.92μmである。 (4) The precursor powder is burned at 750 ° C. for 4 hours, and after dispersion and selection after the resulting powder, a ceria-based composite abrasive powder product is obtained. In content 70 wt% of ceria therein, the content of magnesium oxide is 1.5 wt%, the content of fluorine at 6.8 wt%, D 50 of the abrasive powder is 0.92 .mu.m.
実施例10
(1)塩化ランタンセリウムプラセオジム混合溶液と炭酸水素マグネシウム溶液とを所定の速度で同時に反応装置に加入するとともに、少量なリン酸を加入し、炭酸水素マグネシウムの加入量は理論量の116%で、反応温度は25℃、1h撹拌する。
Example 10
(1) The lanthanum cerium chloride praseodymium mixed solution and the magnesium hydrogen carbonate solution are simultaneously added to the reactor at a predetermined rate, and a small amount of phosphoric acid is added. The amount of magnesium hydrogen carbonate added is 116% of the theoretical amount. The reaction temperature is stirred at 25 ° C. for 1 h.
(2)ステップ(1)の混合スラリーを60℃で保温しながら2hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) The mixed slurry of step (1) is aged for 2 h while being kept at 60 ° C., and a precursor powder of polishing powder is obtained through filtration, washing and drying.
(3)前記前駆体粉体を850℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は60.5wt%で、酸化マグネシウムの含有量は0.3wt%で、リンの含有量は0.2wt%で、当該研磨粉のD50は1.8μmである。 (3) The precursor powder is burned at 850 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 60.5 wt%, the content of magnesium oxide is 0.3 wt%, the content of phosphorus is 0.2 wt%, and the D 50 of the polishing powder is 1.8 μm.
実施例11
(1)塩化ランタンセリウムプラセオジム混合溶液と炭酸水素マグネシウム溶液とを所定の速度で同時に反応装置に加入し、炭酸水素マグネシウムの加入量は理論量の110%で、反応温度は25℃、1h撹拌してスラリーが得られる。
Example 11
(1) A lanthanum cerium chloride praseodymium mixed solution and a magnesium hydrogen carbonate solution are simultaneously added to the reaction apparatus at a predetermined rate, and the addition amount of magnesium hydrogen carbonate is 110% of the theoretical amount, and the reaction temperature is stirred at 25 ° C. for 1 hour. To obtain a slurry.
(2)ステップ(1)で得られたスラリーに少量なリン酸ナトリウム加入し、むらなく混合させ、60℃で保温しながら3hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) A small amount of sodium phosphate is added to the slurry obtained in step (1), mixed evenly, aged for 3 hours while keeping at 60 ° C., filtered, washed and dried, and then a precursor powder of polishing powder The body is obtained.
(3)前記前駆体粉体を950℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は58.5wt%で、酸化マグネシウムの含有量は0.08wt%で、リンの含有量は2.6wt%で、当該研磨粉のD50は2.5μmである。 (3) The precursor powder is burned at 950 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 58.5 wt%, the content of magnesium oxide is 0.08 wt%, the content of phosphorus is 2.6 wt%, and the D 50 of the polishing powder is 2.5 μm.
実施例12
(1)塩化ランタンセリウム混合溶液と炭酸水素マグネシウム溶液とを所定の速度で同時に反応装置に加入し、炭酸水素マグネシウムの加入量は理論量の110%で、反応温度は25℃、1h撹拌してスラリーが得られる。
Example 12
(1) The lanthanum cerium chloride mixed solution and the magnesium hydrogen carbonate solution are simultaneously added to the reaction apparatus at a predetermined rate. A slurry is obtained.
(2)ステップ(1)で得られたスラリーに少量なフッ化ナトリウム加入し、むらなく混合させ、60℃で保温しながら3hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) A small amount of sodium fluoride is added to the slurry obtained in step (1), mixed evenly, aged for 3 hours while being kept at 60 ° C., filtered, washed and dried, and then a precursor powder of polishing powder The body is obtained.
(3)前記前駆体粉体を800℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は63.5wt%で、酸化マグネシウムの含有量は0.03wt%で、フッ素の含有量は3.6wt%で、当該研磨粉のD50は1.5μmである。 (3) The precursor powder is burned at 800 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 63.5 wt%, the content of magnesium oxide is 0.03 wt%, the content of fluorine is 3.6 wt%, and the D 50 of the polishing powder is 1.5 μm.
比較実施例2(従来の工程による製造)
(1)塩化ランタンセリウム混合溶液(稀土濃度はREOで計算して90g/Lである)と炭酸水素アンモニウム溶液とを同時に反応装置に加入するとともに、少量なフッ化アンモニウムを加入し、炭酸水素アンモニウムの加入量は理論量の110%で、反応温度は25℃、反応pH値は6.5で、研磨粉理論重量の2%のポリエチレングリコールを加入し、3h撹拌してスラリーが得られる。
Comparative Example 2 (manufacturing by conventional process)
(1) A lanthanum cerium chloride mixed solution (the rare earth concentration is 90 g / L calculated by REO) and an ammonium hydrogen carbonate solution are simultaneously added to the reactor, and a small amount of ammonium fluoride is added to the ammonium hydrogen carbonate. The addition amount of is 110% of the theoretical amount, the reaction temperature is 25 ° C., the reaction pH value is 6.5, 2% polyethylene glycol of the theoretical weight of the abrasive powder is added, and stirred for 3 hours to obtain a slurry.
(2)ステップ(1)のスラリーを、60℃で保温しながら12hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 12 h while being kept at 60 ° C., and a precursor powder of polishing powder is obtained through filtration, washing and drying.
(3)前記前駆体粉体を900℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は63.5wt%で、酸化マグネシウムの含有量は0wt%で、フッ素の含有量は2.2wt%で、当該研磨粉のD50は3.5μmで、(D90−D10)/2D50は2.5である。 (3) The precursor powder is burned at 900 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria composite abrasive powder product is obtained. Among them, the content of ceria is 63.5 wt%, the content of magnesium oxide is 0 wt%, the content of fluorine is 2.2 wt%, and the D 50 of the abrasive powder is 3.5 μm (D 90 -D 10) / 2D 50 is 2.5.
得られるセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行い、その研磨腐食量は0.43mg/minで、引っ掻き傷率は25%である。 The obtained ceria-based composite polishing powder is prepared as a slurry, and a polishing experiment is performed on a flat glass specimen. The polishing corrosion amount is 0.43 mg / min, and the scratch rate is 25%.
研磨腐食量とは、所定のテスト条件において、被検定の稀土研磨粉サンブルがガラスに対して、単位時間、単位面積における研磨量で、引っ掻き傷率とは、高エネルギーハロゲンランプで観察して、ガラスの引っ掻き傷が表面、裏面のいずれにおいても反射し、かつ引っ掻き傷の長さはガラスの半径以上である場合、当該ガラスが引っ掻き傷が存在すると判断し、引っ掻き傷があるガラスの数と被研磨ガラスの数との比は引っ掻き傷率である。 The amount of polishing corrosion is the amount of polishing in the unit time and unit area of the rare earth polishing powder sample to be tested under a predetermined test condition, and the scratch rate is observed with a high energy halogen lamp. If glass scratches are reflected on both the front and back surfaces and the length of the scratch is equal to or greater than the radius of the glass, it is determined that the glass is scratched, and the number of glass with scratches and The ratio to the number of polished glasses is the scratch rate.
実施例13
(1)塩化ランタンセリウム混合溶液(稀土濃度はREOで計算して90g/Lである)と炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して10g/Lである)とを同時に反応装置に加入し、炭酸水素マグネシウムの加入量は理論量の110%で、反応温度は25℃、反応pH値は6.5で、研磨粉理論重量の2%のポリエチレングリコールを加入し、3h撹拌してスラリーが得られる。
Example 13
(1) A lanthanum cerium chloride mixed solution (the rare earth concentration is 90 g / L calculated by REO) and a magnesium hydrogen carbonate solution (the concentration is 10 g / L calculated by magnesium oxide) are simultaneously added to the reactor. The addition amount of magnesium hydrogen carbonate is 110% of the theoretical amount, the reaction temperature is 25 ° C., the reaction pH value is 6.5, 2% of polyethylene glycol of the theoretical weight of the polishing powder is added, and the slurry is stirred for 3 hours. Is obtained.
(2)ステップ(1)のスラリーを、60℃で保温しながら12hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 12 h while being kept at 60 ° C., and a precursor powder of polishing powder is obtained through filtration, washing and drying.
(3)前記前駆体粉体を900℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は65.3wt%で、酸化マグネシウムの含有量は0.01wt%で、当該研磨粉のD50は3.3μmで、(D90−D10)/2D50は1.78であり、形態は球状に近い。 (3) The precursor powder is burned at 900 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria composite abrasive powder product is obtained. Among them, the content of ceria is 65.3 wt%, the content of magnesium oxide is 0.01 wt%, the D 50 of the polishing powder is 3.3 μm, and (D 90 -D 10 ) / 2D 50 is 1 .78 and the shape is nearly spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.35mg/minに達し、引っ掻き傷率は18%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.35 mg / min and the scratch rate was 18%. .
実施例14
(1)塩化ランタンセリウム混合溶液 (稀土濃度はREOで計算して90g/Lである)と炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して10g/Lである)とを同時に反応装置に加入し、少量なフッ化アンモニウムを加入する。炭酸水素マグネシウムの加入量は理論量の110%で、反応温度は25℃、反応pH値は6.5で、研磨粉理論重量の2%のポリエチレングリコールを加入し、3h撹拌してスラリーが得られる。
Example 14
(1) A lanthanum cerium chloride mixed solution (the rare earth concentration is 90 g / L calculated by REO) and a magnesium hydrogen carbonate solution (the concentration is 10 g / L calculated by magnesium oxide) are simultaneously added to the reactor. Add a small amount of ammonium fluoride. The amount of magnesium bicarbonate added is 110% of the theoretical amount, the reaction temperature is 25 ° C., the reaction pH value is 6.5, polyethylene glycol of 2% of the theoretical weight of the polishing powder is added, and stirred for 3 hours to obtain a slurry. It is done.
(2)ステップ(1)のスラリーを、60℃で保温しながら12hエイジングし、濾過や、洗浄、乾燥を経て研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 12 h while being kept at 60 ° C., and a precursor powder of polishing powder is obtained through filtration, washing and drying.
(3)前記前駆体粉体を900℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は65.3wt%で、酸化マグネシウムの含有量は0.01wt%で、フッ素の含有量は2.2wt%で、当該研磨粉のD50は2.6μmで、(D90−D10)/2D50は1.66であり、形態は球状に近い。 (3) The precursor powder is burned at 900 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria composite abrasive powder product is obtained. The content of ceria therein is 65.3wt%, the content of magnesium oxide is 0.01 wt%, the content of fluorine at 2.2 wt%, D 50 of the abrasive powder is 2.6 [mu] m, ( D 90 -D 10) / 2D 50 is 1.66, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.40mg/minに達し、引っ掻き傷率は15%である。 As a result of preparing the obtained ceria-based composite polishing powder as a slurry and conducting a polishing experiment on a flat glass specimen, the amount of polishing corrosion reached 0.40 mg / min, and the scratch rate was 15%. .
実施例15
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製し、稀土含有量はREO(稀土酸化物)で計算して120g/Lである。
Example 15
(1) A mixed solution of cerium chloride and lanthanum chloride is prepared at a predetermined ratio, and the rare earth content is 120 g / L calculated by REO (rare earth oxide).
(2)炭酸水素マグネシウム溶液を沈殿剤として、濃度(酸化マグネシウムで計算)は15h/Lで、均一な速度でステップ(1)の混合溶液に加入し、沈殿させ、炭酸水素マグネシウムの加入量は理論量の105%で、反応温度は20℃、反応pH値は5で、0.5h撹拌して混合溶液が得られる。 (2) Using magnesium hydrogen carbonate solution as a precipitant, the concentration (calculated with magnesium oxide) is 15 h / L, and is added to the mixed solution of step (1) at a uniform rate to cause precipitation. At 105% of the theoretical amount, the reaction temperature is 20 ° C., the reaction pH value is 5, and the mixture is obtained after stirring for 0.5 h.
(3)ステップ(2)の混合溶液を50℃まで加熱して、少量なフッ化ケイ素酸ナトリウムを添加し、保温しながら24hエージングして、濾過、洗浄、乾燥してから、研磨粉の前駆体粉体が得られる。 (3) Heat the mixed solution of step (2) to 50 ° C., add a small amount of sodium fluorosilicate, age for 24 hours while keeping warm, filter, wash and dry, and then polish the polishing powder A body powder is obtained.
(4)前記前駆体粉体を1000℃で3hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は62wt%で、酸化マグネシウムの含有量は0.005wt%で、フッ素の含有量は5wt%で、当該研磨粉のD50は4.8μmで、(D90−D10)/2D50は1であり、形態は球状に近い。 (4) The precursor powder is burned at 1000 ° C. for 3 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 62 wt%, the content of magnesium oxide is 0.005 wt%, the content of fluorine is 5 wt%, and the D 50 of the polishing powder is 4.8 μm, (D 90 -D 10 ) / 2D 50 is 1, and the shape is nearly spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.47mg/minに達し、引っ掻き傷率は14%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.47 mg / min, and the scratch rate was 14%. .
実施例16
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製し、稀土含有量はREOで計算して150g/Lである。
Example 16
(1) A mixed solution of cerium chloride and lanthanum chloride is prepared at a predetermined ratio, and the rare earth content is 150 g / L calculated by REO.
(2)炭酸水素マグネシウム溶液を沈殿剤として、濃度(酸化マグネシウムで計算)は20h/Lで、均一な速度でステップ(1)の混合溶液に加入し、沈殿させ、少量なリン酸アンモニウムを加入する。炭酸水素マグネシウムの加入量は理論量の105%で、反応温度は20℃、反応pH値は5.5で、研磨粉の理論重量の5%のポリエチレングリコールを加入してむらなく混合させ、3h撹拌して混合溶液が得られ、濾過、洗浄、乾燥してから、研磨粉の前駆体粉体が得られる。 (2) Using magnesium hydrogen carbonate solution as a precipitant, the concentration (calculated with magnesium oxide) is 20 h / L, and it is added to the mixed solution in step (1) at a uniform rate to cause precipitation, and a small amount of ammonium phosphate is added. To do. The amount of magnesium bicarbonate added is 105% of the theoretical amount, the reaction temperature is 20 ° C., the reaction pH value is 5.5, and 5% of the theoretical weight of the polishing powder is added to polyethylene glycol and mixed evenly. A mixed solution is obtained by stirring, and after filtering, washing and drying, a precursor powder of an abrasive powder is obtained.
(3)前記前駆体粉体を950℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は62wt%で、酸化マグネシウムの含有量は0.05wt%で、リンの含有量は5wt%で、当該研磨粉のD50は2.5μmで、(D90−D10)/2D50は1.2であり、形態は球状に近い。 (3) The precursor powder is burned at 950 ° C. for 4 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 62 wt%, the content of magnesium oxide is 0.05 wt%, the content of phosphorus is 5 wt%, the D 50 of the abrasive powder is 2.5 μm, and (D 90 -D 10 ) / 2D 50 is 1.2, and the shape is nearly spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.41mg/minに達し、引っ掻き傷率は13%である。 As a result of preparing the obtained ceria-based composite polishing powder as a slurry and conducting a polishing experiment on a flat glass specimen, the amount of polishing corrosion reached 0.41 mg / min, and the scratch rate was 13%. .
実施例17
(1)炭酸水素マグネシウム溶液(酸化マグネシウムで計算して20g/Lである)と塩化セリウムランタン混合溶液 (REOで計算して100g/Lである)とを同時に反応釜に加入し、少量なリン酸ナトリウムを加入する。炭酸水素マグネシウムの加入量は理論量の115%で、反応温度は25℃、反応pH値は7で、、4h撹拌して、研磨粉理論重量の0.1%のポリエチレングリコールを加入しむらなく混合させ、それから熟成タンクに入らせて、70℃で2hエイジングしてから、濾過、洗浄、乾燥し、研磨粉の前駆体粉体が得られる。
Example 17
(1) A magnesium hydrogen carbonate solution (calculated with magnesium oxide and 20 g / L) and a cerium chloride lanthanum mixed solution (calculated with REO and 100 g / L) are simultaneously added to the reaction kettle, and a small amount of phosphorus Add sodium acid. The amount of magnesium bicarbonate added is 115% of the theoretical amount, the reaction temperature is 25 ° C., the reaction pH value is 7, and the mixture is stirred for 4 hours, so that the polyethylene glycol of 0.1% of the theoretical weight of the polishing powder is uniformly added. The mixture is then mixed, then placed in an aging tank, aged at 70 ° C. for 2 h, filtered, washed, and dried to obtain a precursor powder of an abrasive powder.
(2)前記前駆体粉体を700℃で8hバーニングして、得られる粉体に対する分散、選別を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は60wt%で、酸化マグネシウムの含有量は0.5wt%で、リンの含有量は0.1wt%で、当該研磨粉のD50は1.2μmで、(D90−D10)/2D50は0.89であり、形態は球状に近い。 (2) The precursor powder is burned at 700 ° C. for 8 hours, and after dispersion and selection with respect to the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 60 wt%, the content of magnesium oxide is 0.5 wt%, the content of phosphorus is 0.1 wt%, and the D 50 of the polishing powder is 1.2 μm, (D 90 -D 10) / 2D 50 is 0.89, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.36mg/minに達し、引っ掻き傷率は11%である。 As a result of preparing the obtained ceria-based composite polishing powder into a slurry and conducting a polishing experiment on a flat glass specimen, the amount of polishing corrosion reached 0.36 mg / min, and the scratch rate was 11%. .
実施例18
(1)炭酸水素マグネシウム溶液(酸化マグネシウムで計算して15g/Lである)と塩化セリウム混合溶液 (REOで計算して100g/Lである)とを所定の速度で連続して反応釜に加入し、少量なリン酸を加入する。炭酸水素マグネシウムの加入量は理論量の100%で、反応温度は30℃、反応pH値は5で、研磨粉理論重量の3.2%のポリエチレングリコールを加入しむらなく混合させ、5h撹拌し、それから熟成タンクに入らせて、60℃で5hエイジングしてから、濾過、洗浄、乾燥し、研磨粉の前駆体粉体が得られる。
Example 18
(1) Magnesium bicarbonate solution (15 g / L calculated with magnesium oxide) and cerium chloride mixed solution (100 g / L calculated with REO) are continuously added to the reaction kettle at a predetermined rate. And add a small amount of phosphoric acid. The amount of magnesium bicarbonate added is 100% of the theoretical amount, the reaction temperature is 30 ° C., the reaction pH value is 5, and polyethylene glycol of 3.2% of the theoretical weight of the abrasive powder is evenly mixed and mixed for 5 hours. Then, it is placed in an aging tank and aged at 60 ° C. for 5 hours, and then filtered, washed and dried to obtain a precursor powder of an abrasive powder.
(2)前記前駆体粉体を850℃で6hバーニングして、得られる粉体に対する分散、選別を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は99.99wt%で、酸化マグネシウムの含有量は0.005wt%で、リンの含有量は0.001wt%で、当該研磨粉のD50は3.4μmで、(D90−D10)/2D50は1.4であり、形態は球状に近い。 (2) The precursor powder is burned at 850 ° C. for 6 hours, and after dispersion and selection with respect to the obtained powder, a ceria-based composite abrasive powder product is obtained. The content of ceria therein is 99.99 wt%, the content of magnesium oxide is 0.005 wt%, the content of phosphorus in the 0.001 wt%, D 50 of the abrasive powder is 3.4 .mu.m, ( D 90 -D 10) / 2D 50 is 1.4, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.45mg/minに達し、引っ掻き傷率は14%である。 The obtained ceria-based composite polishing powder was prepared into a slurry, and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.45 mg / min and the scratch rate was 14%. .
実施例19
(1)塩化ランタンセリウムプラセオジムネオジム混合溶液 (REOで計算して200g/Lである)と炭酸水素マグネシウム溶液(酸化マグネシウムで計算して25g/Lである)とを同時に反応装置に加入し、少量なフッ化水素を加入する。炭酸水素マグネシウムの加入量は理論量の130%で、反応温度は15℃、反応pH値は8で、研磨粉理論重量の1%のポリエチレングリコールを加入しむらなく混合させ、2h撹拌し、スラリーが得られる。
Example 19
(1) A lanthanum cerium praseodymium neodymium mixed solution (200 g / L calculated by REO) and a magnesium hydrogen carbonate solution (25 g / L calculated by magnesium oxide) are simultaneously added to the reactor, and a small amount is added. Add new hydrogen fluoride. The amount of magnesium hydrogen carbonate added is 130% of the theoretical amount, the reaction temperature is 15 ° C., the reaction pH value is 8, and 1% of polyethylene glycol of the theoretical weight of the polishing powder is uniformly mixed, stirred for 2 hours, and slurry Is obtained.
(2)ステップ(1)のスラリーを30℃で保温しながら48hエイジングして、濾過、乾燥してから、研磨粉の前駆体粉体が得られる。 (2) The slurry in step (1) is aged for 48 hours while being kept at 30 ° C., filtered and dried, and then a precursor powder of an abrasive powder is obtained.
(3)前記前駆体粉体を950℃で6hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は40.5wt%で、酸化マグネシウムの含有量は4.8wt%で、フッ素の含有量は0.2wt%で、当該研磨粉のD50は3.8μmで、(D90−D10)/2D50は1.5であり、形態は球状に近い。 (3) The precursor powder is burned at 950 ° C. for 6 hours, and after dispersion and selection for the obtained powder, a ceria composite abrasive powder product is obtained. The content of ceria therein is 40.5 wt%, the content of magnesium oxide is 4.8 wt%, the content of fluorine at 0.2 wt%, D 50 of the abrasive powder is 3.8 .mu.m, ( D 90 -D 10) / 2D 50 is 1.5, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.44mg/minに達し、引っ掻き傷率は15%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.44 mg / min and the scratch rate was 15%. .
実施例20
(1)塩化セリウム混合溶液 (稀土濃度はREOで計算して20g/Lである)と炭酸水素マグネシウム溶液(酸化マグネシウムで計算して10g/Lである)とを同時に反応装置に加入し、少量なフッ化ナトリウムを加入する。炭酸水素マグネシウムの加入量は理論量の117%で、反応温度は28℃、反応pH値は6.8で、研磨粉理論重量の0.1%のエチレングリコールを加入しむらなく混合させ、2h撹拌し、スラリーが得られる。
Example 20
(1) A cerium chloride mixed solution (the rare earth concentration is 20 g / L calculated by REO) and a magnesium hydrogen carbonate solution (10 g / L calculated by magnesium oxide) are simultaneously added to the reactor, and a small amount is added. To join the new sodium fluoride. The amount of magnesium hydrogen carbonate added is 117% of the theoretical amount, the reaction temperature is 28 ° C., the reaction pH value is 6.8, and ethylene glycol of 0.1% of the theoretical weight of the polishing powder is mixed evenly and mixed for 2 hours. Stir to obtain a slurry.
(2)スラリーを60℃で保温しながら5hエイジングして、濾過、乾燥してから、研磨粉の前駆体粉体が得られる。 (2) A slurry powder is obtained after aging for 5 hours while keeping the slurry at 60 ° C., filtering and drying.
(3)前記前駆体粉体を800℃で5hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は96.7wt%で、プラセオジミアの含有量は1wt%で、酸化マグネシウムの含有量は1wt%で、フッ素の含有量は8wt%で、当該研磨粉のD50は3.3μmで、(D90−D10)/2D50は0.91であり、形態は球状に近い。 (3) The precursor powder is burned at 800 ° C. for 5 hours, and after dispersion and selection for the resulting powder, a ceria-based composite abrasive powder product is obtained. The content of ceria therein is 96.7wt%, the content of praseodymia is 1 wt%, the content of magnesium oxide in 1 wt%, the content of fluorine at 8 wt%, D 50 of the abrasive powder 3 .3 μm, (D 90 -D 10 ) / 2D 50 is 0.91, and the shape is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.43mg/minに達し、引っ掻き傷率は13%である。 The obtained ceria-based composite polishing powder was prepared into a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.43 mg / min and the scratch rate was 13%. .
実施例21
(1)炭酸水素マグネシウムを沈殿剤とし、濃度は酸化マグネシウムで計算して10g/Lであり、その使用量は理論量の110%である。硫酸セリウム溶液を(稀土濃度はREOで計算して5g/Lである)を沈殿剤に加入し、反応させてスラリーを形成させる。それから、少量なリン酸水素ナトリウムとフッ化ナトリウムを加入し、反応温度は25℃、反応pH値は6.4で、研磨粉理論重量の5%のエチレングリコールを加入しむらなく混合させ、1h撹拌し、スラリーが得られる。
Example 21
(1) Magnesium bicarbonate is used as a precipitant, the concentration is 10 g / L calculated with magnesium oxide, and the amount used is 110% of the theoretical amount. A cerium sulfate solution (the rare earth concentration is 5 g / L calculated by REO) is added to the precipitant and reacted to form a slurry. Then, a small amount of sodium hydrogen phosphate and sodium fluoride were added, the reaction temperature was 25 ° C., the reaction pH value was 6.4, and 5% ethylene glycol of the theoretical weight of the polishing powder was uniformly mixed, and 1 h Stir to obtain a slurry.
(2)ステップ(1)のスラリーを90℃で保温しながら2hエイジングして、濾過、乾燥してから、研磨粉の前駆体粉体が得られる。 (2) The slurry of step (1) is aged for 2 h while being kept at 90 ° C., filtered and dried, and then a precursor powder of an abrasive powder is obtained.
(3)前記前駆体粉体を600℃で2hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は94.8wt%で、酸化マグネシウムの含有量は1.15wt%で、フッ素の含有量は0.8wt%で、リンの含有量は0.5wt%で、当該研磨粉のD50は0.5μmで、(D90−D10)/2D50は0.85であり、形態は球状に近い。 (3) The precursor powder is burned at 600 ° C. for 2 hours, and after dispersion and selection for the obtained powder, a ceria-based composite abrasive powder product is obtained. The ceria content is 94.8 wt%, the magnesium oxide content is 1.15 wt%, the fluorine content is 0.8 wt%, and the phosphorus content is 0.5 wt%. The D 50 of the powder is 0.5 μm, the (D 90 -D 10 ) / 2D 50 is 0.85, and the form is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.31mg/minに達し、引っ掻き傷率は7%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.31 mg / min and the scratch rate was 7%. .
実施例22
(1)硝酸セリウム、硝酸ランタンを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して300g/Lである)。
Example 22
(1) Prepare a mixed solution of cerium nitrate and lanthanum nitrate in a predetermined ratio (the rare earth concentration is 300 g / L calculated by REO).
(2)炭酸水素マグネシウム溶液(酸化マグネシウムで計算して25g/L)を沈殿剤とし、その使用量は理論量の120%である。それをステップ(1)の混合溶液と共沈法で反応させて、反応温度は30℃、反応pH値は7.5で、当該スラリーに研磨粉理論重量の3.1%の界面活性剤であるエチレングリコールを加入し、0.5h撹拌し、スラリーが得られる。 (2) A magnesium hydrogen carbonate solution (25 g / L calculated with magnesium oxide) is used as a precipitant, and the amount used is 120% of the theoretical amount. It is reacted with the mixed solution in step (1) by a coprecipitation method, the reaction temperature is 30 ° C., the reaction pH value is 7.5, and the slurry is made up of a surfactant of 3.1% of the theoretical weight of the polishing powder. Some ethylene glycol is added and stirred for 0.5 h to obtain a slurry.
(3)ステップ(2)の混合スラリーを80℃で保温しながら5hエイジングして、その中に少量なリン酸水素アンモニウムを加入し、むらなく混合させ、濾過、乾燥してから、研磨粉の前駆体粉体が得られる。 (3) The mixed slurry of step (2) is aged for 5 hours while being kept at 80 ° C., and a small amount of ammonium hydrogen phosphate is added therein, mixed uniformly, filtered and dried. A precursor powder is obtained.
(4)前記前駆体粉体を750℃で4hバーニングして、得られる粉体に対する分散、選別の後処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は70wt%で、酸化マグネシウムの含有量は1.9wt%で、リンの含有量は2.8wt%で、当該研磨粉のD50は0.02μmで、(D90−D10)/2D50は1.27であり、形態は球状に近い。 (4) The precursor powder is burned at 750 ° C. for 4 hours, and after dispersion and selection after the resulting powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 70 wt%, the content of magnesium oxide is 1.9 wt%, the content of phosphorus is 2.8 wt%, and the D 50 of the polishing powder is 0.02 μm, (D 90 -D 10) / 2D 50 is 1.27, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.20mg/minに達し、引っ掻き傷率は9%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.20 mg / min and the scratch rate was 9%. .
実施例23
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して90g/Lである)。
Example 23
(1) Prepare a mixed solution of cerium chloride and lanthanum chloride at a predetermined ratio (the rare earth concentration is 90 g / L calculated by REO).
(2)フッ化アンモニウムの水溶液を底層水として、まず、フッ化アンモニウムと反応するのに必要とする理論量の100%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して10g/L)を加入し、、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量はフッ化アンモニウムとランタンセリウム混合溶液の必要ととする理論量の合計使用量の110%で、反応温度は25℃、反応pH値は6.5で、研磨粉理論重量の2%のポリエチレングリコールを加入し、3h撹拌してスラリーが得られる。 (2) Using an aqueous solution of ammonium fluoride as bottom layer water, first, a theoretical amount of 100% magnesium hydrogen carbonate solution (concentration calculated with magnesium oxide is 10 g / L) required to react with ammonium fluoride. Theory that the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are simultaneously added in the form of a cocurrent flow, and the added amount of magnesium hydrogen carbonate is required for the mixed solution of ammonium fluoride and lanthanum cerium. 110% of the total amount used, the reaction temperature is 25 ° C., the reaction pH value is 6.5, 2% polyethylene glycol of the theoretical weight of the abrasive powder is added, and stirred for 3 hours to obtain a slurry.
(3)ステップ(2)の前記スラリーを60℃で保温しながら12hエイジングして、濾過、乾燥してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in step (2) is aged for 12 h while being kept at 60 ° C., filtered and dried, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を900℃で4hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は63wt%で、酸化マグネシウムの含有量は0.01wt%で、フッ素の含有量は2.3wt%で、当該研磨粉のD50は2.3μmで、(D90−D10)/2D50は0.63であり、形態は球状に近い。 (4) The precursor powder is burned at 900 ° C. for 4 hours, and the ceria-based composite abrasive powder product is obtained through the dispersion and selection process for the obtained powder. Among them, the content of ceria is 63 wt%, the content of magnesium oxide is 0.01 wt%, the content of fluorine is 2.3 wt%, and the D 50 of the polishing powder is 2.3 μm (D 90 -D 10 ) / 2D 50 is 0.63, and the shape is nearly spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.42mg/minに達し、引っ掻き傷率は6%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.42 mg / min, and the scratch rate was 6%. .
実施例24
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して120g/Lである)。
Example 24
(1) Prepare a mixed solution of cerium chloride and lanthanum chloride at a predetermined ratio (the rare earth concentration is 120 g / L calculated by REO).
(2)フッ化ケイ素酸ナトリウム溶液を底層水として、まず、フッ化ケイ素酸ナトリウムと反応するのに必要とする理論量の100%の炭酸水素マグネシウムの水溶液(濃度は酸化マグネシウムで計算して15g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の105%で、反応温度は20℃、反応pH値は5で、0.5h撹拌してスラリーが得られる。 (2) Using sodium fluoride siliconate solution as the bottom layer water, first, a theoretical amount of 100% magnesium hydrogen carbonate aqueous solution necessary for reacting with sodium fluoride siliconate (concentration is 15 g calculated with magnesium oxide) / L), and the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are simultaneously added in a co-current manner, and the amount of magnesium hydrogen carbonate added is the sum of the theoretical amount required. At 105%, the reaction temperature is 20 ° C., the reaction pH value is 5, and a slurry is obtained by stirring for 0.5 h.
(3)ステップ(2)の前記スラリーを50℃で保温しながら24hエイジングして、濾過、乾燥してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in step (2) is aged for 24 h while being kept at 50 ° C., filtered and dried, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を1000℃で3hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は60wt%で、酸化マグネシウムの含有量は0.005wt%で、フッ素の含有量は5wt%で、当該研磨粉のD50は3.5μmで、(D90−D10)/2D50は0.92であり、形態は球状に近い。 (4) The precursor powder is burned at 1000 ° C. for 3 hours, and the ceria-based composite abrasive powder product is obtained through a dispersion and selection process for the obtained powder. In content 60 wt% of ceria therein, the content of magnesium oxide is 0.005 wt%, the content of fluorine in the 5 wt%, D 50 of the abrasive powder is 3.5 [mu] m, (D 90 -D 10 ) / 2D 50 is 0.92, and the shape is nearly spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.46mg/minに達し、引っ掻き傷率は9%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.46 mg / min and the scratch rate was 9%. .
実施例25
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して150g/Lである)。
Example 25
(1) Prepare a mixed solution of cerium chloride and lanthanum chloride in a predetermined ratio (the rare earth concentration is 150 g / L calculated by REO).
(2)リン酸アンモニウム溶液を底層水として、まず、リン酸アンモニウムと反応するのに必要とする理論量の100%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して20g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の105%で、反応温度は20℃、反応pH値は5.5で、研磨粉の理論量の5%のポリエチレングリコールを加入し、3h撹拌してスラリーが得られ、濾過、洗浄、及び乾燥を経て、研磨粉の前駆体が得られる。 (2) Using ammonium phosphate solution as the bottom layer water, first add 100% of the theoretical amount of magnesium hydrogen carbonate solution required for reaction with ammonium phosphate (concentration calculated with magnesium oxide is 20 g / L). Then, the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are added simultaneously in the form of a cocurrent flow, and the amount of magnesium hydrogen carbonate added is 105% of the total theoretical amount required. The temperature is 20 ° C., the reaction pH value is 5.5, polyethylene glycol of 5% of the theoretical amount of the abrasive powder is added, and the slurry is obtained by stirring for 3 hours. After filtration, washing, and drying, A precursor is obtained.
(3)前記前駆体粉体を950℃で4hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は62wt%で、酸化マグネシウムの含有量は0.05wt%で、リンの含有量は5wt%で、当該研磨粉のD50は2μmで、(D90−D10)/2D50は0.77であり、形態は球状に近い。 (3) The precursor powder is burned at 950 ° C. for 4 hours, and the ceria-based composite abrasive powder product is obtained through the dispersion and selection process for the obtained powder. Among them, the content of ceria is 62 wt%, the content of magnesium oxide is 0.05 wt%, the content of phosphorus is 5 wt%, and the D 50 of the polishing powder is 2 μm, (D 90 -D 10 ) / 2D 50 is 0.77, and the form is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.42mg/minに達し、引っ掻き傷率は7%である。 The obtained ceria-based composite polishing powder was prepared as a slurry, and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.42 mg / min and the scratch rate was 7%. .
実施例26
(1)塩化セリウム、塩化ランタンを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して100g/Lである)。
Example 26
(1) Prepare a mixed solution of cerium chloride and lanthanum chloride in a predetermined ratio (the rare earth concentration is 100 g / L calculated by REO).
(2)リン酸ナトリウム溶液を底層水として、まず、リン酸ナトリウムと反応するのに必要とする理論量の80%の炭酸水素マグネシウムの水溶液(濃度は酸化マグネシウムで計算して20g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の115%で、反応温度は25℃、反応pH値は7で、研磨粉の理論重量の0.1%のポリエチレングリコールを加入し、4h撹拌してスラリーが得られる。 (2) Using sodium phosphate solution as the bottom layer water, first, 80% of the theoretical amount of magnesium hydrogen carbonate aqueous solution required to react with sodium phosphate (concentration calculated as magnesium oxide is 20 g / L) Then, the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are simultaneously added in the form of a cocurrent flow, and the amount of magnesium hydrogen carbonate added is 115% of the total theoretical amount required, The reaction temperature is 25 ° C., the reaction pH value is 7, and 0.1% of polyethylene glycol of the theoretical weight of the polishing powder is added and stirred for 4 hours to obtain a slurry.
(3)ステップ(2)の前記スラリーを70℃で保温しながら2hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in step (2) is aged for 2 h while being kept at 70 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を700℃で8hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は60wt%で、酸化マグネシウムの含有量は0.5wt%で、リンの含有量は0.1wt%で、当該研磨粉のD50は1.8μmで、(D90−D10)/2D50は0.65であり、形態は球状に近い。 (4) The precursor powder is burned at 700 ° C. for 8 hours, and a ceria-based composite abrasive powder product is obtained through dispersion and selection processing on the obtained powder. Among them, the content of ceria is 60 wt%, the content of magnesium oxide is 0.5 wt%, the content of phosphorus is 0.1 wt%, and the D 50 of the polishing powder is 1.8 μm, (D 90 -D 10) / 2D 50 is 0.65, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.38mg/minに達し、引っ掻き傷率は6%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.38 mg / min and the scratch rate was 6%. .
実施例27
(1)塩化セリウム溶液を調製する(稀土濃度はREOで計算して100g/Lである)。
Example 27
(1) A cerium chloride solution is prepared (the rare earth concentration is 100 g / L calculated by REO).
(2)リン酸溶液を底層水として、まず、リン酸と反応するのに必要とする理論量の100%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して15g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の100%で、反応温度は30℃、反応pH値は5で、研磨粉の理論重量の3.2%のポリエチレングリコールを加入し、5h撹拌してスラリーが得られる。 (2) Using phosphoric acid solution as bottom layer water, first, 100% of a theoretical amount of magnesium hydrogen carbonate solution required to react with phosphoric acid (concentration calculated with magnesium oxide is 15 g / L), Then, the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate were added simultaneously in the form of a cocurrent flow, the amount of magnesium hydrogen carbonate added was 100% of the total theoretical amount required, and the reaction temperature was At 30 ° C. and a reaction pH value of 5, polyethylene glycol of 3.2% of the theoretical weight of the abrasive powder is added and stirred for 5 hours to obtain a slurry.
(3)前記ステップ(2)の前記スラリーを60℃で保温しながら5hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in the step (2) is aged for 5 hours while being kept at 60 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を850℃で6hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は99.99wt%で、酸化マグネシウムの含有量は0.005wt%で、リンの含有量は0.003wt%で、当該研磨粉のD50は2.3μmで、(D90−D10)/2D50は0.8であり、形態は球状に近い。 (4) The precursor powder is burned at 850 ° C. for 6 hours, and the ceria-based composite abrasive powder product is obtained through the dispersion and selection process for the obtained powder. The content of ceria therein is 99.99 wt%, the content of magnesium oxide is 0.005 wt%, the content of phosphorus in the 0.003 wt%, D 50 of the abrasive powder is 2.3 .mu.m, ( D 90 -D 10) / 2D 50 is 0.8, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.42mg/minに達し、引っ掻き傷率は7%である。 The obtained ceria-based composite polishing powder was prepared as a slurry, and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.42 mg / min and the scratch rate was 7%. .
実施例28
(1)塩化ランタンセリウムプラセオジムネオジム溶液を調製する(稀土濃度はREOで計算して200g/Lである)。
Example 28
(1) A lanthanum cerium praseodymium neodymium solution is prepared (the rare earth concentration is 200 g / L calculated by REO).
(2)フッ化水素溶液を底層水として、まず、フッ化水素と反応するのに必要とする理論量の50%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して25g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の130%で、反応温度は15℃、反応pH値は8で、研磨粉の理論重量の1%のポリエチレングリコールを加入し、2h撹拌してスラリーが得られる。 (2) Using hydrogen fluoride solution as the bottom water, first add 50% of the theoretical amount of magnesium hydrogen carbonate solution required for reaction with hydrogen fluoride (concentration calculated as magnesium oxide is 25 g / L). Then, the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are added simultaneously in the form of a cocurrent flow, and the addition amount of magnesium hydrogen carbonate is 130% of the total use amount of the required theoretical amount. The temperature is 15 ° C., the reaction pH value is 8, polyethylene glycol of 1% of the theoretical weight of the polishing powder is added, and the mixture is stirred for 2 hours to obtain a slurry.
(3)前記ステップ(2)の前記スラリーを30℃で保温しながら48hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in step (2) is aged for 48 hours while being kept at 30 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を950℃で6hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は40wt%で、酸化マグネシウムの含有量は5wt%で、フッ素の含有量は0.2wt%で、当該研磨粉のD50は5μmで、(D90−D10)/2D50は1であり、形態は球状に近い。 (4) The precursor powder is burned at 950 ° C. for 6 hours, and after the dispersion and selection process for the obtained powder, a ceria-based composite abrasive powder product is obtained. Among them, the content of ceria is 40 wt%, the content of magnesium oxide is 5 wt%, the content of fluorine is 0.2 wt%, and the D 50 of the polishing powder is 5 μm, (D 90 -D 10 ) / 2D 50 is 1, and the form is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.48mg/minに達し、引っ掻き傷率は10%である。 The obtained ceria-based composite polishing powder was prepared into a slurry, and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.48 mg / min, and the scratch rate was 10%. .
実施例29
(1)稀土濃度はREOで計算して20g/Lである塩化セリウム溶液を調製する。
Example 29
(1) A cerium chloride solution having a rare earth concentration calculated by REO of 20 g / L is prepared.
(2)フッ化ナトリウム溶液を底層水として、まず、フッ化ナトリウムと反応するのに必要とする理論量の70%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して10g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の117%で、反応温度は28℃、反応pH値は6.8で、研磨粉の理論重量の0.1%のエチレングリコールを加入し、2h撹拌してスラリーが得られる。 (2) Using sodium fluoride solution as the bottom layer water, first add 70% of the theoretical amount of magnesium hydrogen carbonate solution required for reaction with sodium fluoride (concentration is 10 g / L calculated with magnesium oxide) Then, the mixed solution of step (1) and the magnesium hydrogen carbonate aqueous solution were simultaneously added in a co-current manner, and the magnesium hydrogen carbonate addition amount was 117% of the total theoretical usage amount required. The temperature is 28 ° C., the reaction pH value is 6.8, 0.1% ethylene glycol of the theoretical weight of the polishing powder is added, and the mixture is stirred for 2 hours to obtain a slurry.
(3)前記ステップ(2)の前記スラリーを60℃で保温しながら5hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in the step (2) is aged for 5 hours while being kept at 60 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を800℃で5hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は97.5wt%で、酸化マグネシウムの含有量は1wt%で、フッ素の含有量は8wt%で、当該研磨粉のD50は3μmで、(D90−D10)/2D50は0.81であり、形態は球状に近い。 (4) The precursor powder is burned at 800 ° C. for 5 hours, and the ceria-based composite abrasive powder product is obtained through a dispersion and selection process for the obtained powder. The content of ceria therein is 97.5 wt%, the content of magnesium oxide in 1 wt%, the content of fluorine at 8 wt%, D 50 of the abrasive powder is 3μm, (D 90 -D 10) / 2D 50 is 0.81, and the form is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.44mg/minに達し、引っ掻き傷率は7%である。 The obtained ceria-based composite polishing powder was prepared into a slurry, and a polishing experiment was performed on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.44 mg / min and the scratch rate was 7%. .
実施例30
(1)稀土濃度はREOで計算して10g/Lである硫酸セリウム溶液を調製する。
Example 30
(1) A cerium sulfate solution having a rare earth concentration of 10 g / L calculated by REO is prepared.
(2)リン酸水素ナトリウムとフッ化ナトリウムとの混合溶液を底層水として、まず、リン酸水素ナトリウムとフッ化ナトリウムと反応するのに必要とする理論量の100%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して5g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の110%で、反応温度は25℃、反応pH値は6.4で、研磨粉の理論重量の3.1%のエチレングリコールを加入し、1h撹拌してスラリーが得られる。 (2) Using a mixed solution of sodium hydrogen phosphate and sodium fluoride as the bottom layer water, first, a theoretically 100% magnesium hydrogen carbonate solution (concentration required for reacting with sodium hydrogen phosphate and sodium fluoride (concentration) 5 g / L (calculated with magnesium oxide) is added, and then the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are added simultaneously in the form of a cocurrent flow. 110% of the total theoretical amount used, the reaction temperature is 25 ° C., the reaction pH value is 6.4, ethylene glycol of 3.1% of the theoretical weight of the polishing powder is added, and the slurry is stirred for 1 hour. can get.
(3)前記ステップ(2)の前記スラリーを90℃で保温しながら2hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in the step (2) is aged for 2 h while being kept at 90 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を600℃で2hバーニングして、得られる粉体に対する分散、選別処理を経て、セリア系複合研磨粉製品が得られる。その中のセリアの含有量は95wt%で、酸化マグネシウムの含有量は1.15wt%で、フッ素の含有量は0.7wt%で、リンの含有量は0.5wt%で、当該研磨粉のD50は0.75μmで、(D90−D10)/2D50は0.57であり、形態は球状に近い。 (4) The precursor powder is burned at 600 ° C. for 2 h, and a ceria-based composite abrasive powder product is obtained through dispersion and selection processing on the obtained powder. Among them, the content of ceria is 95 wt%, the content of magnesium oxide is 1.15 wt%, the content of fluorine is 0.7 wt%, the content of phosphorus is 0.5 wt%, D 50 is 0.75 μm, (D 90 -D 10 ) / 2D 50 is 0.57, and the form is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.32mg/minに達し、引っ掻き傷率は3%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.32 mg / min and the scratch rate was 3%. .
実施例31
(1)硝酸セリウム、硝酸ランタンを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して300g/Lである)。
Example 31
(1) Prepare a mixed solution of cerium nitrate and lanthanum nitrate in a predetermined ratio (the rare earth concentration is 300 g / L calculated by REO).
(2)リン酸水素アンモニウム溶液を底層水として、まず、リン酸水素アンモニウムと反応するのに必要とする理論量の100%の炭酸水素マグネシウムの水溶液(濃度は酸化マグネシウムで計算して25g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の110%で、反応温度は30℃、反応pH値は7.5で、研磨粉の理論重量の5%のエチレングリコールを加入し、0.5h撹拌してスラリーが得られる。 (2) Using ammonium hydrogen phosphate solution as the bottom layer water, first, 100% of the theoretical amount of magnesium hydrogen carbonate aqueous solution required for reaction with ammonium hydrogen phosphate (concentration calculated as magnesium oxide is 25 g / L Then, the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are simultaneously added in a co-current form, and the amount of magnesium hydrogen carbonate added is 110% of the total theoretical amount required. The reaction temperature is 30 ° C., the reaction pH value is 7.5, 5% ethylene glycol of the theoretical weight of the polishing powder is added, and the mixture is stirred for 0.5 h to obtain a slurry.
(3)前記ステップ(2)の前記スラリーを80℃で保温しながら5hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in the step (2) is aged for 5 hours while being kept at 80 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を750℃で4hバーニングして、得られる粉体に対する分散、選別処理を経て、前記セリア系複合研磨粉が得られる。その中のセリアの含有量は70wt%で、酸化マグネシウムの含有量は2wt%で、リンの含有量は3wt%で、当該研磨粉のD50は0.04μmで、(D90−D10)/2D50は0.73であり、形態は球状に近い。 (4) The precursor powder is burned at 750 ° C. for 4 hours, and the ceria-based composite polishing powder is obtained through dispersion and selection processing on the obtained powder. Among them, the content of ceria is 70 wt%, the content of magnesium oxide is 2 wt%, the content of phosphorus is 3 wt%, and the D 50 of the polishing powder is 0.04 μm, (D 90 -D 10 ) / 2D 50 is 0.73, and the form is almost spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.26mg/minに達し、引っ掻き傷率は5%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.26 mg / min and the scratch rate was 5%. .
実施例32
(1)硝酸セリウムを所定の比率で混合溶液に調製する(稀土濃度はREOで計算して60g/Lである)。
Example 32
(1) Prepare a mixed solution of cerium nitrate at a predetermined ratio (the rare earth concentration is 60 g / L calculated by REO).
(2)フッ化ナトリウム溶液を底層水として、まず、フッ化ナトリウムと反応するのに必要とする理論量の60%の炭酸水素マグネシウム溶液(濃度は酸化マグネシウムで計算して13g/L)を加入し、それからステップ(1)の混合溶液と炭酸水素マグネシウムの水溶液とを並流の形で同時に加入し、炭酸水素マグネシウムの加入量は必要ととする理論量の合計使用量の115%で、反応温度は25℃、反応pH値は7で、研磨粉の理論重量の2.5%のエチレングリコールを加入し、3h撹拌してスラリーが得られる。 (2) Using sodium fluoride solution as the bottom water, first, add 60% of the theoretical amount of magnesium hydrogen carbonate solution required for reaction with sodium fluoride (concentration calculated with magnesium oxide is 13 g / L). Then, the mixed solution of step (1) and the aqueous solution of magnesium hydrogen carbonate are added simultaneously in the form of a cocurrent flow, and the addition amount of magnesium hydrogen carbonate is 115% of the total usage amount of the required theoretical amount. The temperature is 25 ° C., the reaction pH value is 7, and 2.5% ethylene glycol of the theoretical weight of the abrasive powder is added and stirred for 3 hours to obtain a slurry.
(3)前記ステップ(2)の前記スラリーを65℃で保温しながら8hエイジングして、濾過、洗浄してから、研磨粉の前駆体粉体が得られる。 (3) The slurry in the step (2) is aged for 8 hours while being kept at 65 ° C., filtered and washed, and then a precursor powder of an abrasive powder is obtained.
(4)前記前駆体粉体を900℃で3hバーニングして、得られる粉体に対する分散、選別処理を経て、前記セリア系複合研磨粉が得られる。その中のセリアの含有量は99wt%で、酸化マグネシウムの含有量は0.1wt%で、フッ素の含有量は0.5wt%で、当該研磨粉のD50は0.05μmで、(D90−D10)/2D50は0.8であり、形態は球状に近い。 (4) The precursor powder is burned at 900 ° C. for 3 hours, and the ceria-based composite polishing powder is obtained through dispersion and selection processing on the obtained powder. Among them, the content of ceria is 99 wt%, the content of magnesium oxide is 0.1 wt%, the content of fluorine is 0.5 wt%, and the D 50 of the polishing powder is 0.05 μm, (D 90 -D 10) / 2D 50 is 0.8, the form is close to spherical.
得られたセリア系複合研磨粉をスラリーに調製して、平らなガラス検体に対して研磨実験を行った結果、その研磨腐食量は0.25mg/minに達し、引っ掻き傷率は2%である。 The obtained ceria-based composite polishing powder was prepared as a slurry and subjected to a polishing experiment on a flat glass specimen. As a result, the amount of polishing corrosion reached 0.25 mg / min and the scratch rate was 2%. .
以上は本発明の好適な実施例に過ぎず、本発明を限定するものではない。当業者であれば、本発明の様々な変更や変形が可能である。本発明の精神や原則を逸脱しないいずれの変更、置換、改良なども本発明の保護範囲内に含まれる。 The above are only preferred embodiments of the present invention, and do not limit the present invention. Those skilled in the art can make various modifications and variations of the present invention. Any changes, substitutions, improvements, etc. that do not depart from the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (19)
(1)研磨粉の主要成分であるセリウムを含有する塩溶液をむらなく混合するステップと、
(2)炭酸水素マグネシウムの水溶液を沈殿剤として、ステップ(1)の混合溶液にむらなく混合させ、スラリーを得るステップと、
(3)ステップ(2)のスラリーを30℃〜90℃で保温しながら0〜48hエイジングし、濾過して研磨粉の前駆体粉体を得るステップと、
(4)前駆体粉体を600℃〜1000℃でバーニングされて、得られる粉体に対する分散、選別の後処理を経て、マグネシウム元素を、酸化マグネシウムで計算して0.005wt%〜5wt%含有するセリア系複合研磨粉製品を得るステップと、を含むことを特徴とするセリア系複合研磨粉の製造方法。 A method for producing a ceria-based composite abrasive powder,
(1) A step of uniformly mixing a salt solution containing cerium which is a main component of the polishing powder;
(2) Using an aqueous solution of magnesium bicarbonate as a precipitant, uniformly mixing the mixed solution of step (1) to obtain a slurry;
(3) Aging the slurry in step (2) at a temperature of 30 ° C. to 90 ° C. for 0 to 48 h, filtering to obtain a polishing powder precursor powder,
(4) The precursor powder is burned at 600 ° C. to 1000 ° C., and after dispersion and selection post-treatment on the obtained powder, the magnesium element is calculated from magnesium oxide and contained in an amount of 0.005 wt% to 5 wt%. And a step of obtaining a ceria-based composite abrasive powder product.
Precipitate and collect the CO 2 generated by the roasting process recovered, method for producing ceria composite abrasive powder according to claim 13, characterized in that used in the production of magnesium hydrogen carbonate solution.
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